CN1328267C

CN1328267C - Method for producing purified epoxy compound

Info

Publication number: CN1328267C
Application number: CNB97115595XA
Authority: CN
Inventors: 塚本裕敏; 大野隆己; 池田久男; 日高基彦
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 1996-07-19
Filing date: 1997-07-21
Publication date: 2007-07-25
Anticipated expiration: 2017-07-21
Also published as: EP0822189B1; CN1172806A; KR980009252A; ATE226948T1; US5892065A; EP0822189A3; AU2852497A; EP0822189A2; KR100390563B1; DE69716680T2; DE69716680D1; AU714033B2

Abstract

A 2,3-epoxypropyl derivative or a 2-methyl-2,3-epoxypropyl derivative of a compound having carboxyl groups or amido groups is produced as a purified product having an epoxide equivalent of 1.0 to 1.1 times the theoretical epoxide equivalent of the derivative, an ionic halogen content of 10 ppm or less, transparency when molten and a stability against increase in the epoxide equivalent when stored at 150 DEG C. for 24 hours, by a process comprising steps (A) reacting 1.2 to 60 mol of an epihalohydrin or a 2-methyl-epihalohydrin with 1 mol of active hydrogen atoms of the carboxyl or amido group of the compound in the presence of a particular catalyst, thereby forming a reaction product containing a 2-hydroxy-3-halopropyl derivative or a 2-hydroxy-2-methyl-3-halopropyl derivative, (B) dehydrohalogenating the derivative by adding to the reaction product a sufficient amount of an alkali metal hydroxide thereby forming a final slurry containing the 2,3-epoxypropyl derivative of the 2-methyl-2,3-epoxypropyl derivative and the alkali metal halide, (C) washing the final slurry or a liquid product formed by removing the alkali metal halide from the final slurry thereby forming a refined liquid containing the derivative, and (D) removing by evaporation the epihalohydrin or the 2-methyl-epihalohidrin from the refined liquid, thereby forming the 2,3-epoxypropyl derivative or the 2-methyl-2,3-epoxypropyl derivative as the purified product.To produce an epoxy compound having a molecular structure having whole active hydrogen atoms substituted with epoxypropyl groups, as a high purity industrial product from a compound having carboxyl group or amide group in the molecule.

Description

The method for preparing the purified epoxy compounds

The present invention relates to has 2 to production, 3-epoxypropyl or 2-methyl-2, the improvement of the method for the purified product of the epoxy compounds of 3-epoxypropyl, particularly to the compound of 2-4 carboxyl or 1-3 amido is arranged from its molecule, produce 2 effectively, 3-epoxypropyl derivative or 2-methyl-2, the method of the purified product of 3-epoxypropyl derivative, all carboxyl or the hydrogen atom in the amido are by 2 in these derivatives, 3-epoxypropyl or 2-methyl-2, the 3-epoxypropyl replaces, and purified product can form transparent and stable liquid when fusing.

United States Patent (USP) 3,859,314 have disclosed a kind of method of producing polycarboxylic glycidyl ester, it comprises makes poly carboxylic acid and Epicholorohydrin reaction, polycarboxylic per 1 mole of carboxyl at least with the reaction of 2 moles Epicholorohydrin, use tertiary amine, tertiary ammonium salt or quaternary ammonium compound as catalyzer in the reaction, become 0 in the 150-2000_ reaction up to acid number, then, at 90-130_, removing by evaporation under the reduction pressure of the water that produces in the dehydrohalogenation, in ester, add a kind of alkali metal hydroxide gradually, make the chloroethene alcohol ester hydrohalogenation of generation.

The specification sheets of this patent discloses an embodiment, having prepared epoxy equivalent (weight) is 152, chloride content is 0.8% m-phthalic acid diglycidyl ether, this method comprises the product of dehydrohalogenation of the chloroethene alcohol ester of water cleaning shop phthalic acid, Epicholorohydrin is removed in distillation under reduced pressure from product then.Epoxy equivalent (weight) is high 1.09 times than theoretical value 139.

The Japan open JP-B-44-20323 of unexamined patent has disclosed the method for the N-Racemic glycidol radical derivative of the compound that a kind of preparation contains amido, it be included in halogenation _ existence under, make the compound reaction of amido, handle the reaction product that produces with alkali cpd then.The disclosure discloses in an embodiment, by water, biphosphate sodium water solution, clean the product that obtains with distilled water then, under reduced pressure, 110 ℃, from the product after this cleaning, remove the yield that the method for volatiles can 89% and obtain triglycidyl isocyanurate, the finished product that crystallization obtains from the methanol solution of 50% weight of this product, the epoxy equivalent (weight) of per 100 gram products is 0.92, cl content is 1.0% weight, when the finished product 100 ℃ of heating after 115 hours, the epoxy equivalent (weight) of the finished product reduces by 10%.

Japan has examined and has disclosed a kind of method that is used to prepare the product of triglycidyl isocyanurate among the publication JP-B-45-22751, it comprises, in the presence of catalyzer, make tricarbimide and the quite Epicholorohydrin reaction of its 6-30 molar weight doubly at 60-165 ℃ as tertiary amine, quaternary ammonium hydroxide or quaternary amine; The thick alkali metal hydroxide aqueous solution that adds excessive 5-40% on the stoichiometry; Stir down, the aqueous sodium hydroxide solution of water, biphosphate sodium water solution or dilution is that water cleans the reaction product that produces at last; Remove Epicholorohydrin with rotatory evaporator then.In this disclosed embodiment, disclosed per 1 kilogram of product and contained the oxygen of 9.49-9.8 moles of ethylene oxide and the chlorine of 0.5-1.1%.

United States Patent (USP) 3,198,241 have disclosed the method for separating and reclaim this non-volatile substance from the mixture of non-volatile material fluid and volatile matter, it comprises, repeatedly allow fluid flow downward by action of gravity, form fluidic film and the heat exchange by heat exchange medium at vertical heat-exchanger surface, from the fluid film evaporation of volatile substances that falls.

United States Patent (USP) 4,395, the 542 a kind of methods that disclose, to contain at least 2, the triglycidyl isocyanurate of the Epicholorohydrin of 000ppm and relevant volatile matter is heated to is enough to make it to flow, but can not make its pyrolytic temperature, as 143-159 ℃, then under action of gravity the tower by being filled with the fine rule net or under 1-500mmHg at least once by multistage stripping tower, carry out multistage stripping, obtain to contain at most the Epicholorohydrin of 10ppm and the triglycidyl isocyanurate product of relevant volatile matter.

The epoxy compounds product that is obtained by these usual ways can only be used for general purposes, for example, and as the raw material of polyester lacquer.Yet, to the demand of the highly purified epoxy compounds product that is used for various uses in continuous growth.Particularly, be used for since these epoxy compoundss since the tackiness agent and solder resist of semiconductor encapsulant, electroconductibility connection, requirement provides highly purified poly carboxylic acid, or in its molecule, have at least an amido compound 2,3-epoxypropyl derivative or 2-methyl-2,3-epoxypropyl derivative is to be used for these purposes.Above-mentioned common production method combines with known method of purification, provides to have satisfied the product that high purity requires in a way.For example, repeatedly water clean in the process of aforesaid method, obtain 2, the Epicholorohydrin solution of 3-epoxypropyl derivative or 2-methyl-2, the 2-methyl epichlorohydrin solution of 3-epoxypropyl derivative, or make as 2 of the product of these methods, 3-epoxypropyl derivative or 2-methyl-2,3-epoxypropyl derivative recrystallization repeatedly in as the alcohol of methyl alcohol can improve the purity of product.

But because when water cleans, these glycidyl esters and the meltage of N-glycidyl compound in water are bigger, press above-mentioned water wash products repeatedly, can reduce the yield of product.Above-mentioned recrystallization method of purification is not suitable for the amorphous epoxy compounds yet.When this method was used for the product of crystal rings oxygen compound, because this method almost can not be removed insoluble impurity thin in the product, this method can not reach purified completely to cause product to form transparent melt when melting.

Examined the production method that is disclosed among the publication JP-B-45-22751 in Japan, the method for in the end removing Epicholorohydrin is that efficient is not high, because use rotatory evaporator to make the yield of product quite low.Therefore, this method can not be used for large-scale industrial production.Examined in the method that publication JP-B-44-20323 disclosed in Japan, under reduced pressure, finally removed Epicholorohydrin, but this discloses the method for evaporating that can improve product purity in open by evaporating.

At United States Patent (USP) 3,198, the method that discloses in 241 form downward fluid film because will allow fluid flow downward under action of gravity, and high viscosity fluid is difficult to form at short notice film as the triglycidyl isocyanurate that contains the lower concentration Epicholorohydrin.In the method that this United States Patent (USP) disclosed, must repeatedly repeat to form fluid film at high temperature.Therefore, not only need to remove for a long time Epicholorohydrin, and, reduce the purity of product probably at high like this temperature and the long-time product of maintenance down.

At United States Patent (USP) 4,395, in 542 methods that disclose, because fluid flows downward under action of gravity, high viscosity fluid can not form film by flowing downward as the triglycidyl isocyanurate that contains the lower concentration Epicholorohydrin.With United States Patent (USP) 3,198, passing through of disclosing in 241 forms the method for evaporating of downward fluid film and compares, and multistage steam stripped method of evaporating can be removed Epicholorohydrin at short notice.But high-molecular weight compounds can be bonded to the stripper inwall, thereby stops heat exchange to be carried out smoothly or the product behind the stripping is polluted by insolubles, particularly when carrying out this method in main equipment.The product that particularly contains such insoluble substance can cause many problems, and when being used for the moulded parts of transparent resin, the moulded parts that obtains has low transparency, and maybe when as when lacquer, what obtain difference shows filming of slickness.

The purpose of this invention is to provide a kind of method, can produce 2 from the compound that contains 2-4 carboxyl or 1-3 amido effectively, 3-epoxypropyl derivative or 2-methyl-2, the Industrial products of 3-epoxypropyl derivative, carboxyl in the compound or all hydrogen atoms in the amido are all by 2,3-epoxypropyl or 2-methyl-2, and the 3-epoxypropyl replaces, these Industrial products have high ethylene oxide oxygen level, high thermal stability and low content of halide ions, can form transparent liquid when fusing.

The invention provides 2 of a kind of compound that is used to produce 2-4 carboxyl or 1-3 amido, 3-epoxypropyl derivative or 2-methyl-2, the method of the refined product of 3-epoxypropyl derivative, this product has 1.0-1.1 epoxy equivalent (weight) and the 10ppm or the lower content of halide ions doubly of the theoretical epoxy equivalent (weight) value of derivative, when 150 ℃ store 24 hours after, epoxy equivalent (weight) increases by 3% at most, and this method comprises step (A)-(D):

(A) make epihalohydrin or 2-methyl epihalohydrin and the compound reaction that 2-4 carboxyl or 1-3 amido are arranged, in reaction mixture, the ratio of described compound and epihalohydrin or 2-methyl epihalohydrin is that per 1 mole of active hydrogen atom of the carboxyl of compound or amido is to 1.2-60 mole epihalohydrin or 2-methyl epihalohydrin, tertiary amine, quaternary ammonium hydroxide or the salt, three that also contain catalytic quantity replace phosphine or season _ salt, contain the 2-hydroxyl-3-halopropyl derivative of this compound or the reactor product of 2-hydroxy-2-methyl-3-halopropyl derivative thereby form;

(B) in reaction product, add alkali metal hydroxide gradually, add ratio be with respect to compound described in the reaction product before step (A) reaction per 1 mole of carboxyl or the active hydrogen atom of amido, add 1-2 moles of hydrogen oxide compound, stir the slurry that contains sedimentary alkali metal halide that produces simultaneously, to cause and to finish dehydrohalogenation is derivative, contain 2 of this compound thereby form, 3-epoxypropyl derivative or 2-methyl-2, the final slurry of 3-epoxypropyl derivative and the alkali metal halide that produces by dehydrohalogenation;

(C) be used as sulfonic acid, the sulfonate of finishing agent, the carboxylate salt that at least 7 carbon atoms are arranged, the sulfuric acid of alcohol that at least 4 carbon atoms are arranged or the aqueous solution of its mixture (they have 1% weight solubleness at least in 30 ℃ of water), the final slurry of cleaning step (B) gained, or clean the product liquid from the final slurry of step (B) gained, removed alkali metal halide and to have obtained, the quantity of contained finishing agent described slurry of purifying or product liquid effectively in the described aqueous solution, thus the purification that contains the derivative of formation in step (B) formed; With

(D) remove in step (C) epihalohydrin or 2-methyl epihalohydrin in the purification that obtains by evaporation, thereby form 2 of compound, 3-epoxypropyl derivative or 2-methyl-2, the purified product of 3-epoxypropyl derivative.

In the present invention, the epoxy equivalent (weight) of epoxy compounds product is defined as the product weight (gram) of the oxyethane Sauerstoffatom that contains 1 mole.

Sample solution with the ion chromatography product, measure the content of halide-ions in the product, its expression is present in content of halide ions in the product with the form of salt, being prepared as of sample solution, product is dissolved in the liquid mixture of 100 weight part acetonitriles and 25 parts by weight of purified water, or with this liquid mixture extracted products.

The thermostability of representing product by the per-cent of product product epoxy equivalent (weight) before the epoxy equivalent (weight) difference of 150 ℃ of heating before and after 24 hours and heating in sealed vessel.The percentage ratio that epoxy equivalent (weight) increases is more little, and the thermostability of product is high more.

After the degassing, the kaolin turbidity of melt is represented the turbidity of product melt.The kaolin turbidity is defined as, when guaranteeing the kaolin of level and the mixture of 10 milliliter of 37 weight % formalin, dilutes 1 gram with pure water, the kaolin solution deciding grade and level of 10ppm is 1, the kaolin solution deciding grade and level of 20ppm is 2, the kaolin solution deciding grade and level of 30ppm is 3, and the kaolin solution deciding grade and level of 50ppm is 4.Kaolin turbidity with the kaolin turbidity grade representative products melt of the kaolin solution of identical turbidity.The kaolin turbidity of product melt is more little, and the purity of product is high more.The kaolin turbidity be 1 or littler product be transparent substantially.

The product that obtains in the step (D) of the invention described above is highly refined product, has the 1.0-1.1 epoxy equivalent (weight) doubly that is equivalent to the theoretical epoxy equivalent (weight) of described derivative, have corresponding to maximum 3% the thermostabilitys that increase of epoxy equivalent (weight), content of halide ions is 10ppm or lower, during fusing, the kaolin turbidity is 1 to the maximum.

The used starting compound that 2-4 carboxyl arranged of step (A) can be any compound that generally can be used as the epoxy compound raw material.For example, that can mention has an aliphatic dicarboxylic acid, as toxilic acid, succsinic acid, methylene-succinic acid, fumaric acid, hexanodioic acid, pimelic acid, suberic acid, sebacic acid or from the dipolymer acid or the trimer acid of unsaturated fatty acids; Aromatic dicarboxylic acid is as phthalic acid, m-phthalic acid, terephthalic acid, tetrahydrophthalic acid, hymic acid, tetrachlorophthalic acid, hexahydrophthalic acid, phenylene-diacetic acid or naphthalic acid; The aromatic tricarboxylic acid, as 1,2,4-benzenetricarboxylic acid or 1,3,5-benzenetricarboxylic acid; And the aromatic acid, as 1,2,4, the 5-pyromellitic acid.Because a carboxyl has an active hydrogen atom, a dicarboxylic acid, a tricarboxylic acid and a tetracarboxylic acid molecule have 2,3 and 4 active hydrogen atoms respectively.As long as can react, also can be used as at the employed compound that carboxyl is arranged of step (A) by these acid anhydrides that have the compound of carboxyl to obtain.Active hydrogen atom number in such acid anhydrides of 1 molecule equals the quantity of all carboxyls of the acid anhydrides hydrolyzate of 1 molecule.The example that the compound of 2-4 carboxyl is arranged preferably is phthalic acid, m-phthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid and 1,2,4,5-pyromellitic acid.

As the compound that 1-3 amido arranged, can use common as the epoxy compound raw material those.That for example, can mention has N, N '-dimethyl urea, N, N '-diphenyl urea, ethylidene-urea, glycolylurea and an isocyanuric acid.Wherein, preferred glycolylurea and isocyanuric acid.Ethylidene-urea, N, N '-dimethyl urea and N, N '-diphenyl urea respectively have an amido and two active hydrogen atoms.Glycolylurea has two amidos and two active hydrogen atoms.Isocyanuric acid has three amidos and three active hydrogen atoms.

As epihalohydrin, that can mention has Epicholorohydrin, epibromohydrin, an epiiodohydrin.Wherein, because it is easy to obtain preferred Epicholorohydrin.To 2-methyl epihalohydrin, that can mention has 2-methyl epichlorohydrin, 2-methyl epibromohydrin and a 2-methyl epiiodohydrin.From the angle that is easy to obtain, preferred 2-methyl epichlorohydrin.

As catalyzer, can use phosphine, season _ compound of amine, quaternary ammonium compound, replacement etc.Though,, replace phosphine and season _ salt but preferred catalyzer is tertiary amine, quaternary ammonium hydroxide, quaternary ammonium salt, three can use as the primary amine of butylamine with as the secondary amine of dibutylamine.

Preferred catalyzer is, tertiary amine for example is as triethylamine, Tri-n-Propylamine, Tributylamine, benzyldimethylamine or triethanolamine salt; Quaternary ammonium hydroxide is as tetramethylammonium hydroxide or hydroxide benzyl TMA (TriMethylAmine); Quaternary ammonium salt is as zephiran chloride TMA (TriMethylAmine), acetate benzyl TMA (TriMethylAmine), methyl chloride three second ammoniums, tetramethylammonium chloride or tetraethylammonium chloride; Three replace phosphine, as triphenylphosphine, trimethylphenyl phosphine or tributylphosphine; Season _ salt, as the Diethylaminoethyl triphenyl _, the methyl chloride triphenyl _, the tonsilon triphenyl _, the iodate methyl triphenyl _, bromination benzyl triphenyl _ or bromination ethyl triphenyl _.Wherein, preferred tetramethylammonium chloride, tetraethyl-ammonium bromide and bromination ethyl triphenyl _.When with terephthalic acid during, can use alkali metal halide as Sodium Bromide as catalyzer as raw material.

The example of alkali metal hydroxide has, sodium hydroxide, potassium hydroxide, lithium hydroxide.Wherein, preferred sodium hydroxide and potassium hydroxide.Such alkali metal hydroxide preferably uses with thick aqueous solution form, and for example, with 20-70 weight %, preferably the concentration of 40-60 weight % is used.

In step (A), can use four types raw material.Form by above-mentioned compound and epihalohydrin for first kind by carboxyl, form by above-mentioned compound and 2-methyl epihalohydrin for second kind by carboxyl, the third is made up of above-mentioned compound and epihalohydrin by amido, is made up of above-mentioned compound and 2-methyl epihalohydrin by amido for the 4th kind.No matter use any raw material, the consumption of epihalohydrin or 2-methyl epihalohydrin is, with respect to 1 mole at the compound that carboxyl is arranged or active hydrogen atom in the compound of amido is arranged, use 1.2-60 mole epihalohydrin or 2-methyl epihalohydrin, be preferably the 2-20 mole, be preferably the 5-10 mole.

At step (A), there are the compound of carboxyl or amido and epihalohydrin or 2-methyl epihalohydrin to carry out addition reaction, be formed with the 2-hydroxyl-3-halopropyl derivative or the 2-hydroxy-2-methyl-3-halopropyl derivative of the compound of carboxyl or amido.Therefore, those above-mentioned dicarboxylic acid can form its two (2-hydroxyl-3-halopropyl) ester or its two (2-hydroxy-2-methyl-3-halopropyl) ester respectively, those above-mentioned tricarboxylic acid can form its three (2-hydroxyl-3-halopropyl) ester or its three (2-hydroxy-2-methyl-3-halopropyl) ester respectively, and those above-mentioned tetracarboxylic acids can form its four (2-hydroxyl-3-halopropyl) ester or its four (2-hydroxy-2-methyl-3-halopropyl) ester respectively.On the other hand, those above-mentioned urea derivativess can form its N respectively, N '-two (2-hydroxyl-3-halopropyl) derivative or its N, N '-two (2-hydroxy-2-methyl-3-halopropyl) derivative, glycolylurea can form its N respectively, N '-two (2-hydroxyl-3-halopropyl) derivative or its N, N '-two (2-hydroxy-2-methyl-3-halopropyl) derivative, isocyanuric acid can form its three (2-hydroxyl-3-halopropyl) ester or its three (2-hydroxy-2-methyl-3-halopropyl) ester respectively.

Although the addition reaction in the step (A) can be carried out in the presence of the catalyzer not having, be preferably the material that use can accelerated reaction, come accelerated reaction.Can use various materials,,, stronger relatively active catalyzer be arranged to above-mentioned as sodium hydroxide from relatively low active alkali metal hydroxide is arranged.But, preferably use above-mentioned preferred catalyzer to come accelerated reaction.Therefore, addition reaction is preferably in 60-130 ℃ under heating, carries out in replace the reaction mixture that phosphines or season _ salt forms by above-mentioned raw material with as the tertiary amine of catalyzer, quaternary ammonium hydroxide, quaternary ammonium salt, three.Catalyst consumption is the 0.001-0.1 mole by per 1 mole of compound that carboxyl or amido are arranged, and is preferably the ratio of 0.01-0.05 mole.Above mol ratio also may be used on catalyzer when the alkali metal halide that uses during as reaction raw materials with terephthalic acid.In the superincumbent reaction mixture, be benchmark, begin to add the water of 0.1-2 weight % in reaction, with accelerated reaction with epihalohydrin or 2-methyl epihalohydrin.

Reaction mixture is heated to the active hydrogen atom at least 90% that makes the compound that carboxyl or amido are arranged in the reaction mixture, preferably all disappears.For example, can adopt liquid-phase chromatographic analysis to come active hydrogen atom in the detection reaction mixture.Therefore, general by heating 2-10 hour, can produce the reaction product that contains epihalohydrin and above-mentioned 2-hydroxyl-3-halopropyl derivative, or contain the reaction product of 2-methyl epihalohydrin and above-mentioned 2-hydroxy-2-methyl-3-halopropyl derivative.

In step (B), 2-hydroxyl-3-halopropyl derivative and by product 2-hydroxyl-1 in the reaction product that step (A) obtains, 3-two Halopropanes, or 2-hydroxy-2-methyl-3-halopropyl derivative and by product 2-hydroxy-2-methyl-1,3-two Halopropanes experience dehydrohalogenation, discharge hydrogen halide, become epoxy compounds.

Therefore, in reaction, by product 2-hydroxyl-1,3-two Halopropanes form epihalohydrin, and 2-hydroxy-2-methyl-1,3-two Halopropanes form 2-methyl epihalohydrin.

On the other hand, two (2-hydroxyl-3-halopropyl) ester of the dicarboxylic acid that produces in step (A) forms two (2 of dicarboxylic acid, the 3-epoxypropyl) ester, two (2-hydroxy-2-methyl-3-halopropyl) ester of dicarboxylic acid forms two (2-methyl-2,3-epoxypropyl) ester of this carboxylic acid.

Similar, tricarboxylic three (2-hydroxyl-3-halopropyl) ester forms tricarboxylic three (2, the 3-epoxypropyl) ester, and tricarboxylic three (2-hydroxy-2-methyl-3-halopropyl) ester forms tricarboxylic three (2-methyl-2,3-epoxypropyl) ester.

Four (2-hydroxyl-3-halopropyl) ester of tetracarboxylic acid forms four (2, the 3-epoxypropyl) ester of tetracarboxylic acid, and four (2-hydroxy-2-methyl-3-halopropyl) ester of tetracarboxylic acid forms four (2-methyl-2,3-epoxypropyl) ester of tetracarboxylic acid.

The N of the derivative of urea, N '-two (2-hydroxyl-3-halopropyl) derivative forms the N of urea derivatives, N '-two (2, the 3-epoxypropyl) derivative, the N of the derivative of urea, N '-two (2-hydroxy-2-methyl-3-halopropyl) derivative forms the N of urea derivatives, N '-two (2-methyl-2,3-epoxypropyl) derivative.

The N of glycolylurea, N '-two (2-hydroxyl-3-halopropyl) derivative forms the N of glycolylurea, N '-two (2, the 3-epoxypropyl) derivative, the N of glycolylurea, N '-two (2-hydroxy-2-methyl-3-halopropyl) derivative forms the N of glycolylurea, N '-two (2-methyl-2,3-epoxypropyl) derivative.

Three (2-hydroxyl-3-halopropyl) ester of isocyanuric acid forms three (2, the 3-epoxypropyl) ester of isocyanuric acid, and three (2-hydroxy-2-methyl-3-halopropyl) ester of isocyanuric acid forms three (2-methyl-2,3-epoxypropyl) ester of isocyanuric acid.

In step (B), in the reaction product that step (A) obtains, progressively add, preferably drip alkali metal hydroxide, be preferably the aqueous solution of its 20-70 weight %, be more preferably the aqueous solution of 40-60 weight %, by the 1 mole carboxyl of compound in the reaction product before carrying out addition reaction or the active hydrogen atom of amido, to the oxyhydroxide of 1-2 mole, the ratio that is preferably the oxyhydroxide of 1-1.2 mole adds, simultaneously epihalohydrin or the 2-methyl epihalohydrin in the back flow reaction product.In adding the alkali metal hydroxide process, above-mentioned dehydrohalogenation takes place, in reaction mixture, produce alkali metal halide and water.The alkali metal halide crystallization obtains containing the slurry of sedimentary alkali metal halide.When being the sprotic polar solvent of the 3-30 weight % of benchmark with epihalohydrin or 2-methyl epihalohydrin, exist down as dimethyl formamide or methyl iso-butyl ketone (MIBK), when carrying out dehydrohalogenation, but accelerated reaction, thereby may reduce the content of the hydrolysis halogen in the product that step (D) in the back obtains.When in the presence of above-mentioned sprotic polar solvent, reacting, although in the reaction mixture of step (A), may add solvent, add solvent again but be preferably in the slurry of step (B), with this reaction of quickening under relatively low temperature, to carry out.

When forming slurry, under reduced pressure, slurry is remained under the alap temperature, as at 10-80 ℃, preferably at 20-70 ℃, water that adds with consecutive evaporation and the generation water in slurry with epihalohydrin or 2-methyl epihalohydrin, and with the gas condensation of condenser with evaporation, the water of condensation is discharged outside the reaction mixture, and the epihalohydrin or the 2-methyl epihalohydrin of condensation is back in the slurry.And, during adding, keep the vacuum tightness of 100mmHg when being preferably in beginning, and increase vacuum tightness gradually with the carrying out of adding, finally reach about 60mmHg.Generally 1-10 hour completing steps (B) reaction.

Be preferably in and stir the reaction of carrying out step (B) under the slurry.When reacting with small-scale, common stirring such as blade stir or turbine blade just stirs and can satisfy.But when when carrying out the reaction of step (B) on a large scale, when for example the volume of slurry was at least 20 liters, common whipping device was inapplicable.If stir insufficiently, a large amount of accumulation and adhering on the bottom of container and wall of above-mentioned sedimentary alkali metal halide, water and alkali metal hydroxide make the fluid can not smooth flow, thereby stop the smooth evaporation of water.The inadequate stirring meeting of sedimentary alkali metal halide, water and alkali metal hydroxide causes side reaction at the position of its accumulation, thereby causes in the product yield and the purity of subsequently step (C) and acquisition (D) low.But find that when keeping slurry under the abundant stirring that is being enough to prevent sedimentary alkali metal halide, water and alkali metal hydroxide accumulation, the yield of product and purity can remain on high level.

The high speed rotating of depending merely on the agitator that blade or turbine blade are housed can not guarantee slurry effectively, and particularly the slurry of at least 100 liters large volume does not have the accumulation of sedimentary alkali metal halide, water and alkali metal hydroxide.Carry out with reaction, the alkali metal halide precipitation is increased to very high concentration in the slurry, is enough to the agitator of high speed rotating is produced big resistance.Sometimes, the agitator of high speed rotating only can be pressed in sedimentary alkali metal halide, water and alkali metal hydroxide on the wall of container like this.And under the situation of large volume slurry, the water in the slurry is being easy to evaporation near the pulp surface place, but in the boiling hardly of reaction container bottom.Therefore, if sedimentary alkali metal halide, water and alkali metal hydroxide rest on reaction container bottom still, in slurry side reaction can take place.

It is mobile unimportant to produce the high speed slurry, and the stirring that only produces partial circulation in slurry also is that efficient is not high.On the contrary, should be to keep the homodisperse stirring of whole slurry preferably.Stir preferably and be, for example, can make slurry produce the fluid circulation, make fluid rise to the surface of slurry along container inner wall from the bottom, make the fluid of rising be reversed to the fluid of downward eddy current again and cross eddy current and shear, thereby keep slurry even.Existing such can produce such circulating fluid and eddy current, and eddy current is sheared the commodity of fragmented agitator.When the agitator that can carry out so better stirring was used in combination with the reaction vessel that has plate washer, agitator can provide better stirring.

Therefore, when the large volume slurry of handling at least 100 liters, can in container, carry out step (B) by method (B '), method (B ') is included in the reaction product that step (A) obtains adds alkali metal hydroxide gradually, its amount is for carrying out the per 1 mole of active hydrogen atom before the addition reaction by the compound that contains in the reaction product, add the 1-2 mole, be preferably the alkali metal hydroxide of 1-1.2 mole, alkali metal hydroxide is 20-70 weight %, better be the aqueous solution of the concentration of 40-60 weight %, the slurry that contains sedimentary alkali metal halide with formation, under agitation keep slurry, make slurry produce circulating fluid, make fluid rise to the surface of slurry along container inner wall from the bottom, make the fluid of rising be reversed to downward eddy current and cross the eddy current shearing again, thereby slurry is kept evenly, simultaneously under vacuum, from slurry, remove the water of adding and the water of generation at 20-60 ℃ by evaporation, up to finishing dehydrohalogenation, contain the precipitation alkali metal halide with formation, have carboxyl or amido compound 2,3-epoxypropyl derivative and epihalohydrin, or the 2-methyl-2 of compound, the slurry of 3-epoxypropyl derivative and 2-methyl epihalohydrin.Method (B ') has reduced the amount of by-product impurities in reaction product significantly, therefore help three (2 of crystalline derivatives such as isocyanuric acid, the 3-epoxypropyl) ester or three (2-methyl-2, the 3-epoxypropyl) two (2 of ester or terephthalic acid, the 3-epoxypropyl) ester or two (2-methyl-2, the 3-epoxypropyl) production of ester is because can significantly improve the purity of product in the step (E) of back.

As the finishing agent that in step (C), uses, use the water-soluble compound that contains organic group that in 30 ℃ of water, has 1 weight % solubleness at least.If use solubleness in 30 ℃ of water less than the compound that contains organic group of 1 weight % as finishing agent, the compound of the low solubility in the aqueous solution can be moved to contiguous organic layer, and in the product of the collection step that waits behind, reduce the quality of product.Though the solubleness of compound in water that contains organic group reduces with the increase of carbonatoms in its organic group, still preferably contains the compound that organic group and the solubleness in 30 ℃ of water are at least 1 weight %.As finishing agent, if do not mind the reduction of product yield or reduce because of the extra cleaning step of needs causes efficient, although also can use when being dissolved in the water compound for the acid or alkaline aqueous solution, but be the neutral compound in the time of should being preferably dissolved in the water, because it can not cause that such efficient reduces.

To can be used as the compound of finishing agent, sulfuric acid of sulfonic acid, sulfonate, carboxylate salt, alcohol and composition thereof is arranged.The alkyl that these compounds can contain alkyl, amido, ester group, hydroxyl, ether, acetoxyl or be replaced by such group.As above-mentioned salt, preferably can make salt have the monobasic salt of high-dissolvability, for example, an alkali metal salt is as the salt of sodium, potassium or lithium; Amine salt, as Monoethanolamine MEA BASF, diethanolamine or triethanolamine salt or ammonium salt, rather than the salt of polyacid base, as the salt of magnesium, calcium or aluminium.

The example preferably of sulfonic acid comprises Phenylsulfonic acid, the Phenylsulfonic acid of the alkyl replacement of 1-3 carbon atom is arranged, as toluenesulphonic acids and xylene monosulfonic acid and naphthalene monosulfonic acid.

The example preferably of sulfonate is an alkali metal salt, ammonium salt or the amine salt of aromatic sulfonic acid, for example, and an alkali metal salt of Phenylsulfonic acid (as sodium salt), ammonium salt or amine salt (as triethanolamine salt); The Phenylsulfonic acid that the alkyl of 1-3 carbon atom replaces such as an alkali metal salt (as sodium salt) of toluenesulphonic acids are arranged, ammonium salt or amine salt (as triethanolamine salt); The formaldehyde condensation products of such alkyl substituted benzene sulfonate; An alkali metal salt of p-hydroxybenzenyl sulfonate (as sodium salt), ammonium salt or amine salt (as triethanolamine salt); To an alkali metal salt (as sodium salt) of nonyl benzene sulfonic acid, ammonium salt or amine salt (as triethanolamine salt); An alkali metal salt of naphthene sulfonic acid (as sodium salt), ammonium salt or amine salt (as triethanolamine salt); Or the aromatic sulfonic acid an alkali metal salt, as the formaldehyde condensation products of naphthalenesulfonate; An alkali metal salt, ammonium salt or amine salt that the alkansulfonic acid of 10 carbon atoms is arranged at most, for example, an alkali metal salt of methanesulfonic (as sodium salt), ammonium salt or amine salt (as triethanolamine salt); An alkali metal salt of ethane sulfonic acid (as sodium salt), ammonium salt or amine salt (as triethanolamine salt); An alkali metal salt of vinyl sulfonic acid (as sodium salt), ammonium salt or amine salt (as triethanolamine salt), the polymkeric substance of such vinylsulfonate; An alkali metal salt of 2-aminoethane sulphonic acid (as sodium salt), ammonium salt or amine salt (as triethanolamine salt); An alkali metal salt of octyl group sulfoacetic acid (as sodium salt), its ammonium salt or amine salt (as triethanolamine salt); An alkali metal salt of butane sulfonic acid (as sodium salt), ammonium salt or amine salt (as triethanolamine salt); An alkali metal salt of hexane sulfonic acid (as sodium salt), ammonium salt or amine salt (as triethanolamine salt); An alkali metal salt of perfluoroetane sulfonic acid (as sodium salt), ammonium salt or amine salt (as triethanolamine salt); An alkali metal salt of decane sulfonic acid (as sodium salt), ammonium salt or amine salt (as triethanolamine salt).

The example of carboxylate salt is an alkali metal salt that the unit price paraffinic acid of 11 carbon atoms is arranged at most preferably, for example, and an alkali metal salt of enanthic acid (as sodium salt), an alkali metal salt (as sodium salt) of sad an alkali metal salt (as sodium salt) or capric acid; Aromatic monocarboxylate's salt such as Sodium Benzoate, sodium salicylate or Sodium.beta.-phenylacrylate; Two an alkali metal salts of aromatic dicarboxylic acid are as disodium phthalate; Two an alkali metal salts of alicyclic hydrocarbon dicarboxylic acid are as the hexahydro-phthalic acid disodium; An alkali metal salt of hydroxybenzene carboxylic acid is as salicylic acid sodium or P-hydroxybenzoic acid sodium.

The example of Chun sulfuric acid is preferably, an alkali metal salt of butyl sulfuric ester (as sodium salt), ammonium salt or amine salt (as triethanolamine salt); An alkali metal salt of heptyl sulfuric ester (as sodium salt), ammonium salt or amine salt (as triethanolamine salt); An alkali metal salt of octyl group sulfuric ester (as sodium salt), ammonium salt or amine salt (as triethanolamine salt); An alkali metal salt of decyl sulfuric ester (as sodium salt), ammonium salt or amine salt (as triethanolamine salt); An alkali metal salt of lauryl sulfate ester (as sodium salt), ammonium salt or amine salt (as triethanolamine salt); An alkali metal salt of myristyl sulfuric ester (as sodium salt), ammonium salt or amine salt (as triethanolamine salt); The sulfuric acid an alkali metal salt (as sodium salt) of lauryl glycol ether, ammonium salt or amine salt (as triethanolamine salt); The sulfuric acid an alkali metal salt (as sodium salt) of the many glycol ethers of nonylphenol, ammonium salt or amine salt (as triethanolamine salt).Can use the sulfuric acid an alkali metal salt of the alcohol of 10-28 carbon atom, for example the sulfuric acid an alkali metal salt (as sodium salt) of the many glycol ethers of lauryl.

Good especially compound be sodium salt, sylvite, lithium salts, ammonium salt or the triethanolamine salt of Phenylsulfonic acid; The sodium salt of toluenesulphonic acids, sylvite, lithium salts, ammonium salt or triethanolamine salt; The polymkeric substance of the sodium salt of vinyl sulfonic acid, sylvite, lithium salts, ammonium salt or triethanolamine salt or these vinylsulfonates; The sodium salt of lauryl sulfate, sylvite, lithium salts, ammonium salt or triethanolamine salt; The formaldehyde condensation products of the sodium salt of naphthene sulfonic acid, sylvite, lithium salts, ammonium salt or triethanolamine salt; Salicylic sodium salt, sylvite, lithium salts; The sodium salt of styracin, sylvite, lithium salts; The disodium salt of tetrahydrophthalic acid, di-potassium or dilithium salt; Disodium salt, di-potassium or the dilithium salt of phthalic acid, toluenesulphonic acids, Phenylsulfonic acid etc.Use these compounds and can improve the thermostability of the product of collection step afterwards and the transparency of its melt as finishing agent.Best is aromatic sulfonic acid and an alkali metal salt thereof because they can not remain in after in the product of collection step, can make the degradation of purified product hardly.

In step (C), clean slurry and make the alkali metal halide in the slurry, residual catalyzer, residual alkali metal hydroxide move to water layer from slurry by contacting, the liquid after obtaining making with extra care with other impurity.Water layer also contains a small amount of with the former epihalohydrin and 2 that is present in the slurry of solubilised state, 3-epoxypropyl derivative, or 2-methyl epihalohydrin and 2-methyl-2,3-epoxypropyl derivative except these flowable component.Therefore, in refining,, use minimum water favourable, help in the shortest time, finishing cleaning to enhance productivity from the angle of product yield.

When the aqueous solution with above-mentioned compound as finishing agent cleans slurry, can be refining effectively in the short period of time with the water of relatively small amount, can not make finishing agent move to organic layer from water layer, obtain purified liquid, particularly, can reach such degree, make the product of step (D) collection afterwards, when it melted, its kaolin opacity was 1 to the maximum.

Slurry preferably cleans several times, rather than only once.Although the purified effect increases with the consumption of finishing agent, in case its amount surpasses 5 weight %, the increase that no longer is directly proportional of its effect with its amount.When slurry is pressed above-mentioned repeated washing, the aqueous solution that is preferably used in the first time and cleans for the second time, derivative in per 100 weight parts in the slurry, contain the 0.01-5 weight part, be preferably the 0.05-2 weight part, be preferably the finishing agent of 0.1-1 weight part, for preventing that product is subjected to the pollution of finishing agent, the amount of the finishing agent of the aqueous solution that is used for cleaning for the third time, in per 100 weight part derivatives in the slurry, reduce to the 0.001-5 weight part, be preferably the 0.001-2 weight part, be preferably the 0.001-1 weight part.The water yield that at every turn is used for cleaning slurry is slurry 2 preferably, and 3-epoxypropyl derivative or 2-methyl-2, the 0.5-50 of 3-epoxypropyl derivative weight doubly are preferably 1-5 doubly.When the aqueous solution with the relatively low finishing agent of its solubleness in water cleaned, the slurry after the cleaning preferably cleaned with a small amount of pure water again.Slightly acidic neutralizing agent such as SODIUM PHOSPHATE, MONOBASIC can coexist as the aqueous solution that is used for cleaning.The temperature of the aqueous solution that is used to clean is preferably 10-40 ℃, is preferably 20-30 ℃.

Available various known common equipment makes slurry contact with the aqueous solution with intermittent type or continous way, cleans.For example, can in the container of belt stirrer, add slurry and separately add the finishing agent and the water of above-mentioned amount or add its aqueous solution simultaneously, make by stirring that slurry and aqueous cleaning solution are fine to be contacted.Churning time depends on stirring intensity, and general the stirring continues short time, 5-10 minute according to appointment.After the stirring, the liquid in container is left standstill.Time of repose depends on top stirring intensity, but under general stirring state, is 5-60 minute, is 10-30 minute preferably.

Yet, by stirring, in a container, clean pulp layer and may cause still muddy organic layer with the aqueous solution, resemble the situation of having used invalid finishing agent at the aqueous solution.Find, assemble quite easily with the good fine drop that contacts the organic layer that produces of the aqueous solution of cleaning for guaranteeing slurry, form organic layer once more, and the fine drop of the aqueous solution is not easy to assemble, therefore can keeps being dispersed in the organic layer that forms again for a long time and make the organic layer muddiness.Find that also the water layer that forms does not again contain so fine drop of many organic layers of quantity, and when organic layer was collected with the fine drop that is dispersed in the aqueous solution wherein, organic layer can produce the low-purity product after the epihalohydrin of step (D) evaporates from behind.It is believed that moving to drop surface some impurity on every side from organic layer can make drop stably be dispersed in the organic layer.

Find, can produce high purity product effectively by the method for cleaning slurry preferably, this method is included in the slurry tower that to add mean diameter be the aqueous solution droplets of 0.1-10 millimeter, drop is contacted with slurry and rise from the tower of pulp layer, gathering afterwards forms aqueous layer or assembles with the aqueous solution that forms previously, again from the pulp layer fractionate aqueous solutions.Purging method by drop may be used on liquid product, this product is that slurry that contains sedimentary alkali metal halide and the q.s that will obtain in step (B) preferably stir times over the water or the aqueous solution of slurry volume together light and slowly, alkali metal halide with dissolution precipitation, or filtering the slurry that contains sedimentary alkali metal halide, the sedimentary alkali metal halide of removing in the slurry that step (B) obtains obtains.Purging method by means of drop can produce limpid purification preferably, join the top of tower by the drop form that was the 0.1-10 millimeter with the mean diameter with the former aqueous layer that forms in gathering once more, drop is risen once more, repeat afterwards to assemble, also can improve its efficient.Therefore, the most handy method (C ') is carried out step (C), to remove the sedimentary alkali metal halide that obtains in the product, method (C ') is included in the tower of liquid product layer and adds the aqueous solution droplets that contains finishing agent, its mean diameter is the 0.1-10 millimeter, be preferably the 0.3-10 millimeter, drop is risen, in tower, assemble afterwards and form aqueous layer, the adding of repeated droplet in tower, rise and assemble these steps, provide the aqueous solution continuously to product liquid, per 100 weight part derivatives have the finishing agent of 0.01-5 weight part in providing with respect to product liquid in product liquid, thereby form purification.The water yield that provides with finishing agent in method (C ') is about preferably, with respect to 100 weight part derivatives, 50-5000 weight part.But repetition methods (C ').

Method (C ') has high like this purification efficiency, even do not use preferable methods (B ') in step (B), method (C ') be applied in the product liquid that contains a large amount of impurity, also can obtain good refining effect.And, even reduce the amount of finishing agent, method (C ') also can obtain effective refining effect, and can be at organic layer residuary water solution.Can mention as an extreme example, and purging method (C ') promptly use the water that does not contain finishing agent, with respect to organic layer in the stirred vessel and water, leave standstill the long period then, regather the method for organic layer, also can be in the improvement of short period of time generation to refining effect.Particularly, because producing three (2 of crystal derivative such as isocyanuric acid, the 3-epoxypropyl) ester or three (2-methyl-2, the 3-epoxypropyl) ester, or terephthalic acid two (2, the 3-epoxypropyl) ester or two (2-methyl-2, the 3-epoxypropyl) in the situation of ester, purification step afterwards (E) also can improve purity, so the available method that does not contain the water of finishing agent (C '), be that method (C ") is produced these crystal derivatives; and method (C ") be included in the tower of the liquid product layer of removing sedimentary alkali metal halide and obtaining, add the water droplet that does not contain finishing agent, its mean diameter is the 0.1-10 millimeter, be preferably the 0.3-10 millimeter, water droplet is risen from the liquid product layer, in tower, assemble afterwards and form water layer, again with mean diameter 0.1-10 millimeter, the drop that is preferably the 0.3-10 millimeter adds water layer on the top of tower, same subsequently rising and gathering, i.e. the adding of repeated droplet in tower, rise and the accumulative circulation, continuing provides water to liquid product, per 100 weight part derivatives in respect to product liquid have added the water of 50-5000 weight part.Method (C ") can repeat.

Be adopted as the equipment of such method design, can carry out this repeat the to add aqueous solution droplets of mean diameter 0.1-10 millimeter, the method that makes its rising and assemble the formation aqueous layer.For example, this equipment comprises a main cylinder, a round shape holder that is connected to the upper end of main cylinder, another is connected to the round shape holder of main cylinder lower end, covering the lid of top holder and the turning axle that reaches the lower end of main cylinder by the center of covering. its internal diameter of the top holder almost internal diameter with main cylinder is identical, it highly is enough to storing liquid, and a discharge outlet is arranged at an upper portion thereof.By lid, assembled a liquid feed pipe that almost reaches the bottom of top holder.Below its internal diameter of holder and main cylinder much at one, its degree of depth is enough to storing liquid, a discharge outlet is arranged bottom it.The centre of holder has one to pass the liquid feed pipe that its sidewall almost reaches the bottom of turning axle below.Around turning axle, to the upper end of main cylinder, many very porous dishes that have are housed with the constant spacing from the bottom of axle.At the inner side-wall of main cylinder, many toroidal membranes are arranged, between each dish, place a dividing plate. below each plate edge, be furnished with a ring.Have many holes on each dish, the upper surface of Kong Congpan is penetrated into its lower surface, and producing mean diameter by these holes is the drop of 0.1-10 millimeter.When connecting a drive systems on its top, turning axle back and forth rotates with certain angle of rotation.

By being connected to the feeder sleeve of lid, add and water immiscibility to above-mentioned cleaning equipment, the organic fluid that its proportion is big than water is full of half in top holder.When back and forth rotating turning axle, the aqueous solution that will be used to clean is supplied with the feeder sleeve that reaches the stored underneath device.Outlet by feeder sleeve is put into the aqueous solution in the organic fluid, is placed on nethermost armor, by coiling top hole, is formed on the drop in the organic fluid.In the tower of the organic fluid on dish, drop moves upward, and is dispersed in the organic fluid when rising.The dividing plate that is fixed on main cylinder inner wall makes the central motion of dispersive drop to main cylinder, therefore makes droplet congregating, forms solution layer on the ring of nethermost second dish.Afterwards, the aqueous solution is by the hole on second dish in organic fluid, and with the upwards discharging of drop form, then, drop is dispersed in the tower of organic fluid when rising once more.Therefore, rise from the aqueous solution of stored underneath device middle part input, repeating dispersion becomes the gathering of drop and drop, arrives the surface of the organic fluid tower in the superincumbent holder up to solution, at there, is formed on the solution layer on the organic fluid tower and stores.The water-soluble liquid measure that stores on the organic fluid tower increases gradually with the further without interruption of the aqueous solution, and behind the discharge outlet of the holder on the aqueous solution reaches, aqueous solution overflow is discharged from discharge outlet.The organic fluid and the aqueous solution without interruption make organic fluid and the aqueous solution continuously convection current contact.By changing the speed of rotation of turning axle, can adjust the input speed of the organic fluid and the aqueous solution and the drop size of the aqueous solution.Cleaning equipment like this commercialization.

To the cleaning equipment product liquid without interruption and the aqueous solution, product liquid is contacted in cleaning equipment continuously with the aqueous solution, and collect the liquid after making with extra care continuously from the bottom of cleaning equipment.In such purging method, preferably also to the aqueous solution of organic fluid finishing agent without interruption, per 100 weight part derivatives in respect to organic fluid have the finishing agent of 0.01-5 weight part.Such cleaning equipment may be used on using in the method (C ") of the water that does not contain finishing agent.

Therefore, in step (C), can prepare the purification that contains epihalohydrin, as being the solution of 70-90 weight % under the situation of Epicholorohydrin.

At step (D), by evaporation, can remove epihalohydrin in the purification that is obtained or 2-methyl epihalohydrin and a small amount of other volatile constituent, there is not the product of these volatile constituents with formation.Steam is introduced condenser, and collects with liquid form.

By the evaporation of epihalohydrin or 2-methyl epihalohydrin, purification is concentrated, for example, can be undertaken by common distillation tower, rotatory evaporator, flasher or falling-film evaporator.Yet during near 10 weight %, liquid can become very thickness with the concentration of epihalohydrin or 2-methyl epihalohydrin.Particularly, when the concentration of epihalohydrin in the liquid or 2-methyl epihalohydrin becomes when being lower than 1 weight %, the velocity of evaporation of these volatile constituents descends suddenly, therefore is difficult to remove effectively these volatile constituents.Find that the abundant purified liquid that obtains in step (C) when the concentration of these volatile constituents is lower than 10 weight %, even when being lower than 1 weight %, can descend the oxyethane oxygen level at 100-165 ℃ of high temperature.Can think that the reduction of oxyethane oxygen level refers residual at the trace impurity that inadequate cleaning caused of step (C).Yet when using the aqueous solution of the finishing agent do not contain abundant amount, the wash number that increases in the step (C) also is difficult to guarantee to remove impurity fully, and can be reduced in the yield of the product that step (D) obtained.Therefore, for obtaining only to contain the purification of acceptable small amount of impurities, preferably will there be the aqueous solution of the finishing agent of high refining effect to be used for the refining of step (C), at step (D), can the short period of time remove these volatile constituents liquid after refining or its enriched material, to obtain not contain substantially the product of these volatile constituents.

Discovery is by being heated to the purification or its enriched material that contain epihalohydrin or 2-methyl epihalohydrin that its concentration of coating on 100-165 ℃ the base material is preferably 1-60 weight % at one, form thickness less than 500 microns fluid film, these volatile constituents are evaporated rapidly from film, thereby be reduced in the concentration of the volatile constituent on the film.Yet forming the film that is thinner than 30 microns from purification or its enriched material is that efficient is not high, because, the corresponding increase of surface-area of the film that forms by purification or its enriched material of unit weight.According to an embodiment preferably of the present invention, by being heated on 100-165 ℃ the base material, by spreader coating purification or its enriched material, forming thickness is the 30-500 micron, is preferably the film of 100-450 micron.And by under reduced pressure, the pressure that is preferably in volatile constituent is to the maximum under the condition of 5mmHg, from the above-mentioned volatile constituent of film evaporation, might be reduced in the concentration of the volatile constituent on the film at short notice.

The concentration of the volatile constituent in the fluid film can be reduced to and make film not have the degree of these volatile constituents substantially, promptly is lower than 100ppm weight.Particularly pass through continuous heating film, but also can pass through more efficient methods, the evaporating volatile component can make volatile constituent be reduced to the weight less than 10ppm.

According to embodiment preferably of the present invention, can remove the volatile constituent in purification or its enriched material effectively by method (D '), method (D ') comprise, surface coated purification or its enriched material at base material, forming thickness is the 30-500 micron, be preferably the film of 100-450 micron, end at film, the concentration of the volatile constituent in purification or its enriched material is the highest, and reduce gradually, at the other end of relative film, concentration is minimum, at 100-165 ℃, be preferably 120-160 ℃, pressure in component is 5mmHg or lower, for example under the 0.1-5mmHg, from film evaporating volatile component, end at the film that its maximum concentration is arranged provides purification or its enriched material continuously simultaneously, and the liquid under will evaporating is sent to the relative the other end gradually and film thickness is increased, and reclaims the final liquid that has than low volatility component concentration from the relative the other end of film continuously.

According to method (D '), might be at short notice, remove epihalohydrin, 2-methyl epihalohydrin and other volatile constituents in the purification that step (C) obtains, reach the degree that does not contain volatile constituent substantially, and might significantly suppress the formation of insoluble substance, these insoluble substances are keeping high temperature to produce when removing volatile constituent probably.Therefore, do not adopting any one preferable methods (B '), preferable methods (C ') and wherein using under the situation of method (C ") of no finishing agent; carrying out the purification that contains a large amount of impurity that step (B) and step (C) are produced, may produce the product that does not contain insoluble substance by method (D ').Particularly, producing the crystal derivative, as three (2 of isocyanuric acid, the 3-epoxypropyl) ester or three (2-methyl-2, the 3-epoxypropyl) two (2, the 3-epoxypropyl) ester or (2-methyl-2 of ester, or terephthalic acid, the 3-epoxypropyl) under the situation of ester, the insoluble substance in the above-mentioned product that obtains in step (D) can not be removed in the purification step (E) of back.Yet if the product that obtains in step (D) does not contain insoluble substance, (E) just can obtain higher purity in purification step.Therefore, method (D ') is preferably used in the product of producing these crystal derivatives.

Removing the method for volatile constituent preferably can successfully carry out by means of the vaporizer that aims at this design.For example, this vaporizer comprises a cylinder, and cylinder is had the lid of a liquid-inlet and a vapour outlet to cover by one, in the cylinder bottom liquid exit is arranged.Around cylinder, a chuck is arranged, cylinder is connected to the vacuum fan that has condenser by vapour outlet with the circulation heating medium.In cylinder, turning axle by lid is arranged, and one is fixed on the dish on a top and below dish a spreader is arranged, described spreader is installed in the end that is fixed in the anchor clamps on the axle by a spring, or is placed on certain clearance the anchor clamps of the end that is fixed in the rod that goes out from shaft extension.By the control of spring or the centrifugal force in the rotation, make spreader press to the inwall of cylinder, place spreader like this, make its rotation with turning axle, slide along cylinder inner wall.Spreader is a rectangular shape, in the face of cylinder has a vertical long plane.On the surface from the top to the bottom, cut out many grooves at interval with constant, groove is with respect to the horizontal plane certain angle crosscut surface.Spreader is pressed to temperature of film in the input speed, vaporizer of strength, purification or its enriched material of vaporizer inwall etc. by regulating spring, can be adjusted in the thickness of the film that forms on the cylinder inner wall.By the liquid-inlet that covers, purification or its enriched material are fed on the dish in cylinder, the centrifugal force during by disc spins makes its edge along dish flow direction dish, reaches the top of cylinder inner wall.The plane of applied device spreads on the cylinder inner wall, forms film at cylinder inner surface.Along with purification without interruption or its enriched material, at the planar edge of the spreader of facing cylinder, it mixes with film in contact, transmits downwards along the cylinder inner wall by chute simultaneously.Therefore, with the rotation of turning axle, purification without interruption or its enriched material are to form film at whole cylinder inner wall.

When evaporating volatile component from the film of purification or its enriched material, with the rotation of turning axle purification without interruption or its enriched material.Therefore, the cycle that liquid film upgrades is identical with the cycle that spreader passes through, and the volatile constituent in the film reduces downwards gradually, make in the top of cylinder inner wall concentration the highest, minimum bottom it.When rotation with turning axle, further purification without interruption or its enriched material, that part of film with minimum volatile constituent concentration accumulates at base of evaporator as final liquid.From reclaim the liquid of accumulation in the outlet of base of evaporator.Known have the such vaporizer that can implement evaporation, and commercialization.

For removing volatile constituent from purification or its enriched material by above-mentioned vaporizer, preferably progressively reduce the concentration of volatile constituent, for example, be reduced to for the first time about 2000-4000ppm, the level that in the final product that is producing, does not have volatile constituent then, rather than once concentration is reduced to 100ppm or lower, even to 50ppm or lower.When the recrystallization process refined product by describing later, there is no need to remove the degree of volatile constituent basic non-volatility component to the product by evaporation, product can contain epihalohydrin or the 2-methyl epihalohydrin of the 1000ppm that has an appointment.

By step (D), can produce derivative preferably, for example two of phthalic acid, m-phthalic acid or terephthalic acid (2, the 3-epoxypropyl) esters or two (2-methyl-2,3-epoxypropyl) ester; 1,2,4-benzenetricarboxylic acid or 1,3, three (2, the 3-epoxypropyl) esters or three (2-methyl-2, the 3-epoxypropyl) ester of 5-benzenetricarboxylic acid; The N of glycolylurea, N '-two (2, the 3-epoxypropyl) derivative or N, N '-two (2-methyl-2,3-epoxypropyl) derivative; Product with the purification of three (2, the 3-epoxypropyl) esters or three (2-methyl-2, the 3-epoxypropyl) ester of isocyanuric acid.As mentioned above, in step (A)-(D), can adopt preferable methods respectively, by the preferable methods of the present invention with these preferred steps (A)-(D) combine, but production high purity epoxy compounds.Preferable methods has: a kind of step (B) that comprises step (A), undertaken by method (B '), by method (C ') step (C) of carrying out and the method for step (D); The method of a kind of step (B) that comprises step (A), undertaken by method (B '), step (C) and the step (D) of being undertaken by method (D '); The method of a kind of step (C) that comprises step (A), step (B), undertaken by method (C ') and the step (D) of being undertaken by method (D '), etc.The method of the step (B) that the best way comprises step (A), undertaken by method (B '), the step (C) of being undertaken by method (C ') and the step (D) of being undertaken by method (D ').These preferably method and the best way applicable to large-scale industrial production.Particularly, producing the crystal derivative, for example two (2 of terephthalic acid, the 3-epoxypropyl) three (2 of ester or two (2-methyl-2,3-epoxypropyl) ester, or isocyanuric acid, the 3-epoxypropyl) ester or three (2-methyl-2, the 3-epoxypropyl) under the situation of ester, the method preferably by will not using finishing agent (C ") with these preferably method combine, can produce the high purity product of these derivatives.Such bonded example has, after step (A), in step (B) and (D) respectively in conjunction with the method that has adopted method (B ') and method (D '); Adopt method (B ') respectively and do not use the method for the method (C ") of finishing agent in step (B) and step (C); In step (C) with (D) respectively in conjunction with the method that adopts the method do not use finishing agent (C ") and method (D '); The best way is respectively in conjunction with employing method (B '), the method (C ") of not using finishing agent and method (D ') in step (B), step (C) and step (D).

In the derivative that can obtain by step (D), by the recrystallization at step (E) in step (D) back, the crystalline compounds of can further purifying, as two (2 of terephthalic acid, the 3-epoxypropyl) two of ester, terephthalic acid (2-methyl-2, the 3-epoxypropyl) three (2-methyl-2,3-epoxypropyl) ester of three of ester, isocyanuric acid (2, the 3-epoxypropyl) esters and isocyanuric acid.At step (E), be dissolved in the product that step (D) reclaims, can methyl alcohol, ethanol, propyl alcohol, methyl ethyl ketone, ethyl acetate, benzene toluene or its mixture be as solvent, wherein, particular methanol.To recrystallization, preferably with the boiling point of product, be dissolved in 1-10 doubly on solvent, be preferably 2-6 times in the solvent of product weight, the solution of generation preferably cools off gradually with 2-30 ℃/hour speed of cooling, with the precipitation crystal.Can adopt common method, as filtering, from the sedimentary crystal of solution separating, if desired, the isolating crystal of available same solvent cleaning adopts common method drying then, obtains final product.Product before the finished product are purified than recrystallization has the thermostability of lower epoxy equivalent (weight) and Geng Gao.Step (E) may be used in the large-scale industrial production, and the particularly production of high purity product no matter whether adopted method (B '), (C '), (C ") or (D '), all can be carried out step (E) in step (D) afterwards.

Embodiment 1:

Step (A): put into 20 gram water in 2 liters of glass reaction flasks that the paddle agitator is housed, 5.5 gram tetraethyl-ammonium bromide and 166 gram (1 mole) terephthalic acids form reaction mixture.Then, under agitation the reaction mixture in the flask is heated to improve its temperature.When the temperature of reaction mixture reaches 89 ℃, reaction mixture under atmospheric pressure comes to life, and heating is proceeded 3 hours, and the steam that is produced makes its cooling with a condenser, and the Epicholorohydrin continuous backflow of all liquefaction arrives flask, and the water of liquefaction is emitted from flask.Stop heating when the temperature of reaction mixture reaches 121 ℃, reaction mixture obtains reaction product when being cooled to 45 ℃.Liquid-phase chromatographic analysis confirms that reaction product does not comprise the carboxyl of the terephthalic acid that belongs to parent material.

Step (B): subsequently, beginning entire reaction product of 45 ℃ in flask dropwise adds the NaOH aqueous solution of 176 gram (in 2.2 moles of NaOH) 50% (weight) under decompression 100mmHg, form reaction mixture, water and Epicholorohydrin are evaporated from reaction mixture under vigorous stirring.Vacuum tightness increases gradually, and the steam condenser condenses, the Epicholorohydrin with all liquefaction is back in the flask continuously, and the water of liquefaction is discharged flask.When vacuum tightness reaches 60mmHg, stop dropwise to add and obtaining containing the slurry of precipitation sodium-chlor.Dropwise add and carried out 6 hours.During the dropping, the reaction mixture under stirring is owing to sedimentary sodium-chlor becomes muddy, but whole the maintenance evenly.According to liquid-phase chromatographic analysis, the slurry that obtains like this comprises the compound that contains 2-hydroxyl-3 chloropropyl less than 1% (weight).

Step (C): with resulting whole slurry in the step (B), 600 gram distilled water and 2 gram toluenesulfonic acid sodium salts place in the Glass Containers, stir 5 minutes, leave standstill then 10 minutes.Reclaim all the first layer Epicholorohydrin layers, and water layer is transferred in another container.

The Epicholorohydrin layer that then whole recovery is obtained, (in the distilled water) sodium dihydrogen phosphate of 600 grams, 5% (weight) and 2 gram toluenesulfonic acid sodium salts place and stirred 5 minutes in the Glass Containers and left standstill 10 minutes.Reclaim whole second layer Epicholorohydrin layer, and water layer is transferred in another container.Whole second layer Epicholorohydrin that then recovery is obtained and 800 gram distilled water place in the Glass Containers and stirred 5 minutes, allow it leave standstill again 10 minutes.Reclaim whole final Epicholorohydrin layer as refined liquid.

Step (D): resulting whole Epicholorohydrin layers in the step (C) are put people's rotatory evaporator, under reduced pressure heat to remove Epicholorohydrin.Last 1 hour before stopping to evaporate is in the pressure that is decompressed to 2mmHg and 140 ℃ of heating down.Be cooled to room temperature, reclaim in the vaporizer and obtain 257 gram products.The quantity of product is 92% (is benchmark with raw material terephthalic acid used in the step (A)) corresponding to productive rate by calculating as can be known.

Survey less than chlorion in the product, its epoxy equivalent (weight) is 146, and kaolin turbidity (kaolin turbidity) is 1 or littler when 140 ℃ of fusions, and heating is after 24 hours under 150 ℃ in sealed vessel, and epoxy equivalent (weight) is 148.Be changed to 1.4% by what calculate heating back epoxy equivalent (weight) as can be known.

Step (E): with resulting product fusion in the step (D), get 100 gram melts and under agitation be added to gradually in the 400 gram methyl alcohol that are placed in the flask, form the methanol solution of product.This solution is heated to the reflux temperature of methyl alcohol, was cooled to 5 ℃ through 12 hours then, make and be settled out white crystals in the solution.By filtering white crystal is separated and drying, obtained 75 gram final products.The epoxy equivalent (weight) of final product is 140, and the kaolin turbidity when 140 ℃ of fusions is 1 or littler, and heating is after 24 hours under 150 ℃ in sealed vessel, and epoxy equivalent (weight) is 141, and epoxy equivalent (weight) is changed to 0.7% after being heated as can be known by calculating.

Comparative Examples 1:

To stir by the slurry that embodiment 1 step (B) same procedure obtains, allow its method leave standstill then, but do not use toluenesulfonic acid sodium salt by embodiment 1 step (C).Even after leaving standstill 10 minutes, the Epicholorohydrin layer is still highly muddy.Leave standstill again after 12 hours the Epicholorohydrin layer is reclaimed as the first Epicholorohydrin layer.Do not use toluenesulfonic acid sodium salt in a similar manner and after carrying out washing the second time and leaving standstill 10 minutes, the Epicholorohydrin layer is highly muddy.After leaving standstill 12 hours again, the Epicholorohydrin layer is reclaimed as the second Epicholorohydrin layer.Last washing is not used toluenesulfonic acid sodium salt in a similar manner yet and is carried out, leave standstill 10 minutes after, the Epicholorohydrin layer is highly muddy.After leaving standstill 12 hours again, it is reclaimed as last Epicholorohydrin layer.

Handle this last Epicholorohydrin layer by the mode of embodiment 1 step (D), from vaporizer, reclaim and obtain 251 gram products.Product epoxy equivalent (weight) when 140 ℃ of fusions is 151, and the content of chlorion is 5ppm (weight), and the kaolin turbidity is 2, and heating is after 24 hours down at 150 ℃, and its epoxy equivalent (weight) is 158.Be changed to 4.6% by what calculate epoxy equivalent (weight) as can be known.

Method by embodiment 1 step (E) is handled this product, obtains the exsiccant the finished product of 70 gram white crystals forms.The epoxy equivalent (weight) of final product when 140 ℃ of fusions is 142, and the kaolin turbidity is 2, and after heating 24 hours under 150 ℃ in sealed vessel, its epoxy equivalent (weight) is 145.Be changed to 2% by what calculate epoxy equivalent (weight) as can be known.

Embodiment 2

Step (A) and (B): make the slurry that contains sedimentary sodium-chlor by step (A) and method (B) among the embodiment 1.

Step (C): the method for pressing step among the embodiment 1 (C) reclaims last Epicholorohydrin layer, and difference is to replace 2 gram toluenesulfonic acid sodium salts with 2 gram sodium vinyl sulfonates.

Step (D): handle the whole last Epicholorohydrin layer that in step (C), obtains by the method for step (D) among the embodiment 1, obtain 257 gram products by reclaiming in the vaporizer.Survey less than chlorion in product, the epoxy equivalent (weight) of product is 146, and the kaolin turbidity is 1 or littler when 140 ℃ of fusions, and epoxy equivalent (weight) is 148 after 24 hours and heat under 150 ℃ in sealed vessel.

Embodiment 3

Step (C): the method for pressing step among the embodiment 1 (C) reclaims last Epicholorohydrin layer, and difference is to replace 2 gram toluenesulfonic acid sodium salts with 2 gram perfluorooctane sulfonates.

Step (D): handle the whole last Epicholorohydrin layer that in step (C), obtains by the method for step (D) among the embodiment 1, obtain 257 gram products by reclaiming in the vaporizer.In product, survey less than chlorion, its epoxy equivalent (weight), the kaolin turbidity during 140 ℃ of fusions, and 150 ℃ of epoxy equivalent (weight)s that heat after 24 hours down are all identical with the product that embodiment 1 obtains in sealed vessel.

Embodiment 4

Step (C): the method for pressing step among the embodiment 1 (C) reclaims last Epicholorohydrin layer, and difference is to replace 2 gram toluenesulfonic acid sodium salts with 2 gram ammonium tosylates.

Step (D): the method by step (D) among the embodiment 1 is handled the whole last Epicholorohydrin layer that obtains in step (C), obtains 256 gram products by reclaiming in the vaporizer.Survey less than chlorion in product, the kaolin turbidity was 1 or littler when the epoxy equivalent (weight) of product was 147,140 ℃ of fusions, and epoxy equivalent (weight) is 150 after 24 hours and heat under 150 ℃ in sealed vessel.Be changed to 2% by what calculate epoxy equivalent (weight).

Embodiment 5

Step (A) and (B): repeat step (A) among the embodiment 1, difference is to replace 925 to restrain Epicholorohydrins with 1065 gram 2-methyl epichlorohydrins.When reaching 95 ℃, the temperature of reaction mixture begins the backflow of 2-methyl epichlorohydrin.Reaction mixture finally was heated to 120 ℃ through 8 hours.Method by embodiment 1 step (B) was added to 176 aqueous sodium hydroxide solutions that restrain 50% (weight) in the reaction mixture that remains on 45 ℃ through 6 hours, made the slurry that contains sedimentary sodium-chlor.

Step (C): the method by step (C) among the embodiment 1 is handled the whole slurries that obtain in step (B), and difference is to restrain toluenesulfonic acid sodium salts with 2 gram Phenylsulfonic acid potassios for 2, and reclaims last 2-methyl epichlorohydrin layer.

Step (D): the method by step (D) among the embodiment 1 is handled the whole last 2-methyl epichlorohydrin layer that obtains in step (C), obtains 284 gram products by reclaiming in the vaporizer.Survey less than chlorion in product, the kaolin turbidity when its epoxy equivalent (weight) is 163,140 ℃ of fusions is 1 or littler, and 150 ℃ of epoxy equivalent (weight)s that heat after 24 hours down are 165 in sealed vessel.Be changed to 1.2% by what calculate epoxy equivalent (weight).

Embodiment 6

Step (A): in 2 liters of glass reaction flasks of the agitator that the band blade is housed, add 30 gram water, 5.5 gram Tetramethylammonium chlorides, 1388 gram (15 moles) Epicholorohydrins and 129 gram (1 mole) cyanuric acids form reaction mixture.The reaction mixture that under agitation heats in the flask raises its temperature.When the temperature of reaction mixture reached 89 ℃, reaction mixture came to life under barometric point.Continue heating 5 hours, with the steam cooling that produces, the Epicholorohydrin of whole liquefaction is back in the flask with condenser continuously, the water of liquefaction is discharged outside the flask.When the temperature of reaction mixture reaches 120 ℃, stop heating, it is 45 ℃ reaction product that reaction mixture obtains temperature.In product, survey less than unreacted cyanuric acid.

Step (B): the aqueous sodium hydroxide with 256 grams (counting 3.2 moles by NaOH) 50% (weight) under 100mmHg are added in the above-mentioned reaction product in the flask, form reaction mixture, under vigorous stirring, allow water and Epicholorohydrin from reaction mixture, be evaporated simultaneously.Vacuum tightness is increased gradually, with steam cooling, the Epicholorohydrin of whole liquefaction is back in the flask with condenser continuously, the water of liquefaction is discharged outside the flask.When vacuum tightness reaches 60mmHg, stop to drip, obtain containing the slurry of sedimentary sodium-chlor.Dropping lasts 6 hours.In the dropping process, the reaction mixture under stirring is owing to sedimentary sodium-chlor becomes muddy, but maintenance is evenly whole.Press liquid-phase chromatographic analysis, the quantity of the compound of the contained 2-of having hydroxyl-3-chloropropyl is less than 1% (weight) in the slurry of acquisition.

Step (C): will place in the Glass Containers at whole slurries, 600 gram distilled water and the 2 gram toluenesulfonic acid sodium salts that step (B) obtains and stir 5 minutes, leave standstill then 10 minutes.Reclaim whole first Epicholorohydrin layers, water layer is transferred to another container.

Solution and the 2 gram toluenesulfonic acid sodium salts of the SODIUM PHOSPHATE, MONOBASIC of the Epicholorohydrin layer that will all reclaim again, 600 grams 5% (weight) in distilled water place in the Glass Containers and to stir 5 minutes, leave standstill then 10 minutes.Reclaim whole second Epicholorohydrin layers, water layer is transferred to another container.

Place in the Glass Containers in second Epicholorohydrin layer that will all reclaim again and the 800 gram distilled water and stirred 5 minutes, left standstill then 10 minutes.Reclaim all last Epicholorohydrin layers.

Step (D) will be put into a rotatory evaporator at the whole last Epicholorohydrin layer that step (C) obtains, and under reduced pressure heat to remove Epicholorohydrin.Last 1 hour before stopping to evaporate is to be decompressed to 2mmHg and 140 ℃ of heating.Make the material in the vaporizer be cooled to room temperature then, reclaim and obtain 267 gram products.By the productive rate that calculates product is 90% (calculating according to raw material cyanuric acid used in the step (A)).

Survey less than chlorion in product, the kaolin turbidity was 1 or littler when the epoxy equivalent (weight) of product was 103,140 ℃ of fusions, and epoxy equivalent (weight) is 104 after 24 hours and heat under 150 ℃ in sealed vessel.Be changed to 1% by what calculate heating back epoxy equivalent (weight).

Step (E): with the resulting product fusion of step (D), get 100 gram melts and under agitation be added to gradually in the flask that 400 gram methyl alcohol are housed, form the methanol solution of this product.This solution is heated to the reflux temperature of methyl alcohol, was cooled to 5 ℃ through 12 hours again, make and be settled out white crystals in the solution.By filtering to isolate the crystal of white, its drying is obtained 82 gram final products.

Kaolin turbidity when the epoxy equivalent (weight) of final product is 99,140 ℃ of fusions is 1 or littler, and 150 ℃ of epoxy equivalent (weight)s that heat after 24 hours down are 99 in sealed vessel.Be changed to 0% by what calculate heating back epoxy equivalent (weight).

Comparative Examples 2

The slurry that will obtain by the method for embodiment 6 steps (B) leaves standstill by the method for embodiment 6 steps (C), but does not use toluenesulfonic acid sodium salt.Even after leaving standstill 10 minutes, the Epicholorohydrin layer is still very muddy.After leaving standstill 12 hours again, reclaim the Epicholorohydrin layer as the first Epicholorohydrin layer.Toluenesulfonic acid sodium salt is not used in washing for the second time too, leave standstill 10 minutes after, the Epicholorohydrin layer is still very muddy.After leaving standstill 12 hours again, reclaim the Epicholorohydrin layer as the second Epicholorohydrin layer.Toluenesulfonic acid sodium salt is not used in last washing too, leave standstill 10 minutes after, the Epicholorohydrin layer is still very muddy.After leaving standstill 12 hours again, reclaim the Epicholorohydrin layer as last Epicholorohydrin layer.

Handle last Epicholorohydrin layer by the method for embodiment 6 steps (D), in vaporizer, reclaim and obtain 258 gram products.The epoxy equivalent (weight) of this product is 108, and chloride ion content is 4ppm (weight), and the kaolin turbidity is 3 during 140 ℃ of fusions, and 150 ℃ of epoxy equivalent (weight)s that heat after 24 hours down are 113 in sealed vessel.Be changed to 4.6% by what calculate epoxy equivalent (weight).

Product is pressed the method for embodiment 6 steps (E) and handled, obtain the dry final product of 80 gram white crystals forms.Kaolin turbidity when the final product epoxy equivalent (weight) is 100,140 ℃ of fusions is 2, and epoxy equivalent (weight) is 101 after 24 hours and heat under 150 ℃ in sealed vessel.Be changed to 1% by what calculate epoxy equivalent (weight).

Embodiment 7

Contain the slurry that precipitates sodium-chlor by embodiment 6 steps (A) and the preparation of method (B), difference is with 5.5 gram bromination ethyl triphenyl _ replacement 5.5 gram Tetramethylammonium chlorides.

Step (C): the method recovery by embodiment 6 steps (C) obtains final Epicholorohydrin layer.

Step (D): press the resulting all final Epicholorohydrin layer of method treatment step (C) of embodiment 6 steps (D), reclaim by vaporizer and obtain 265 gram products.Survey less than chlorion in product, the kaolin turbidity the when epoxy equivalent (weight) of product is 104,140 ℃ of fusions is 1 or littler, and 150 ℃ of epoxy equivalent (weight)s that heat after 24 hours down are 105 in sealed vessel.Be changed to 1% by what calculate epoxy equivalent (weight).

Embodiment 8

Step (A) and (B): make by step (A) and method (B) among the embodiment 1 and to contain the slurry that precipitates sodium-chlor.

Step (C): the method for pressing step among the embodiment 1 (C) reclaims last Epicholorohydrin layer, and difference is to replace 2 gram toluenesulfonic acid sodium salts with 2 gram toluenesulphonic acidss.

Step (D): handle the whole last Epicholorohydrin layer that in step (C), obtains by the method for step (D) among the embodiment 1, obtain 255 gram products by reclaiming in the vaporizer.Survey less than chlorion in product, the kaolin turbidity was 1 or littler when the epoxy equivalent (weight) of product was 146,140 ℃ of fusions, and epoxy equivalent (weight) is 148 after 24 hours and heat under 150 ℃ in sealed vessel.Be changed to 1.4% by what calculate epoxy equivalent (weight).

Embodiment 9

Step (C): the method for pressing step among the embodiment 1 (C) reclaims last Epicholorohydrin layer, and difference is to replace 2 gram toluenesulfonic acid sodium salts with 2 gram Sodium Benzoates.

Step (D): handle the whole last Epicholorohydrin layer that in step (C), obtains by the method for step (D) among the embodiment 1, by obtaining 258 gram products in the vaporizer.Survey less than chlorion in product, the kaolin turbidity was 1 or littler when its epoxy equivalent (weight) was 147,140 ℃ of fusions, and epoxy equivalent (weight) is 150 after 24 hours and heat under 150 ℃ in sealed vessel.Be changed to 2% by what calculate epoxy equivalent (weight).

Embodiment 10

Step (A) and (B): make the slurry that contains crystallization sodium-chlor by step (A) and method (B) among the embodiment 1.

Step (C): by the Epicholorohydrin layer that the method for step (C) among the embodiment 1 reclaims to the end, difference is that the triethanolamine salts with 2 gram toluenesulphonic acidss replace 2 gram toluenesulfonic acid sodium salts.

Step (D): handle the whole last Epicholorohydrin layer that in step (C), obtains by the method for step (D) among the embodiment 1, by obtaining 256 gram products in the vaporizer.Survey less than chlorion in product, the kaolin turbidity was 1 or littler when the epoxy equivalent (weight) of product was 147,140 ℃ of fusions, and epoxy equivalent (weight) is 149 after 24 hours and heat under 150 ℃ in sealed vessel.Be changed to 1.4% by what calculate epoxy equivalent (weight).

Embodiment 11

Use 20 liters of glass reactors that the agitator of band blade is housed that the scale of embodiment 1 is amplified 10 times.

Step (A) can successfully be undertaken by the same procedure of embodiment 1.

Step (B) is undertaken by the same procedure of embodiment 1, but in the process that adds aqueous sodium hydroxide solution, the sodium-chlor of partly precipitated begins to accumulate near on the sidewall of reactor bottom.When further adding aqueous sodium hydroxide solution, sedimentary sodium-chlor is cumulative, sticks on the sidewall of reactor.The rotating speed of agitator is improved, continue to add sodium hydroxide, but extremely add when finishing, the sodium hydroxide on the sidewall is not dispersed in the reaction mixture.In the slurry of gained, the content of compound with 2-hydroxyl-3-chloropropyl is less than 1% (weight).Step (C) can successfully be undertaken by the same procedure of embodiment 1.

Step under identical scale (D) can successfully be undertaken by the same procedure of embodiment 1, but productive rate is reduced to 90% a little.The kaolin turbidity was 1 or littler when the epoxy equivalent (weight) of product was 151,140 ℃ of fusions, and epoxy equivalent (weight) is 155 after 24 hours and heat under 150 ℃ in sealed vessel.Be changed to 2.6% by what calculate heating back epoxy equivalent (weight).

Step under identical scale (E) can successfully be undertaken by the same procedure of embodiment 1, but the productive rate of final product is reduced to 72% a little.The epoxy equivalent (weight) of final product is 140, and epoxy equivalent (weight) is 141 after 24 hours and heat under 150 ℃ in sealed vessel.

Embodiment 12

Be equipped with two long 15 centimetres, wide 2 centimetres, the reactor of thick 2 millimeters baffle plate repeats embodiment 11.

Step (A) can successfully be pressed the method for embodiment 11 and be implemented.At step (B), different with embodiment 11, by stirring reaction mixture is kept evenly, sedimentary sodium-chlor can not accumulate and stick on the sidewall.Step (C) and (D) can be undertaken by the method for embodiment 11, the productive rate of product is 93%.The kaolin turbidity was 1 or littler when the epoxy equivalent (weight) of product was 146,140 ℃ of fusions, and epoxy equivalent (weight) is 148 after 24 hours and heat under 150 ℃ in sealed vessel.Be changed to 1.4% by what calculate heating back epoxy equivalent (weight).Carry out step (E) by the method for embodiment 11 and obtain product, productive rate is 75%.

Embodiment 13

The scale of embodiment 6 is amplified 100 times.

Used reactor is that stainless steel is made, and internal volume is 200 liters, be equipped with in it two long 60 centimetres, wide 4 centimetres, thick 4 millimeters baffle plate.Used agitator comprises a rotation axis and two flat blades that are fixed in this.These two flat blades are symmetrical in this installation in comprising the plane of rotating shaft, top 2/3 part of blade is made of grid, and 1/3 following part is a blade.The width of agitator is 0.53 times of reactor interior diameter.

When rotating in the liquid in agitator sinks to reactor, the blade of its lower part orders about the bottom of the flow direction sidewall of reactor bottom, form the laminar flow that goes in ring, this laminar flow rises to liquid level along the sidewall of reactor, it is downward to be back into vortex at liquid level, and the grid of the agitator that is rotated cuts into fragment.So when agitator rotates continuously, liquid under agitation keeps evenly, and agitator makes in the liquid liquid stream that produces circulation, and it rises to pulp surface along internal side wall by the bottom of reactor, make the downward liquid stream of liquid circulation becoming vortex of rising at this place, and it is cut into fragment.

Step (A) can successfully be undertaken by the method for embodiment 6.At step (B), different with embodiment 11, reaction mixture keeps evenly, and sedimentary sodium-chlor can not accumulate and stick on the sidewall of reactor.Step (C) is undertaken by the method for embodiment 6.Step (D) makes product with identical scale by the method for embodiment 6, and productive rate is 90%.The epoxy equivalent (weight) of product is 102, and the kaolin turbidity is 1 or littler when 140 ℃ of fusions, and epoxy equivalent (weight) is 103 after 24 hours and heat under 150 ℃ in sealed vessel.Be changed to 1% by what calculate heating back epoxy equivalent (weight).Carry out step (E) by the method for embodiment 6 and obtain product, productive rate is 82%.The epoxy equivalent (weight) of product is 99, and epoxy equivalent (weight) still is 99 after 24 hours even heat under 150 ℃ in sealed vessel.

Embodiment 14

Step (A): in 20 liters of glass reaction flasks of the agitator that the band blade is housed, add 300 gram water, 55 gram Tetramethylammonium chlorides, 13.88 kilograms of (150 moles) Epicholorohydrins and 1.29 kilograms of (10 moles) cyanuric acids form reaction mixture.The reaction mixture that under agitation heats in the flask raises its temperature.When the temperature of reaction mixture reached 89 ℃, reaction mixture came to life under barometric point.Continue heating 5 hours, with the steam cooling that produces, the Epicholorohydrin of whole liquefaction is back in the flask with condenser continuously, the water of liquefaction is discharged outside the flask.When the temperature of reaction mixture reaches 120 ℃, stop heating, it is 45 ℃ reaction product that reaction mixture obtains temperature.In product, survey less than unreacted cyanuric acid.

Step (B): under the 100mmHg decompression, 2.56 kilograms of (counting 3.2 moles by NaOH) 50% aqueous sodium hydroxide are added in the above-mentioned reaction product that maintains 50 ℃, form reaction mixture, under vigorous stirring, allow water and Epicholorohydrin from reaction mixture, be evaporated simultaneously.Vacuum tightness is increased gradually, with steam cooling, the Epicholorohydrin of whole liquefaction is back in the flask with condenser continuously, the water of liquefaction is discharged outside the reactor.When vacuum tightness reaches 60mmHg, stop to drip, obtain containing the slurry that precipitates sodium-chlor.Dropping lasts 6 hours.After refluxing again 5 minutes, remove vacuum in the reactor, stop to stir.Press liquid-phase chromatographic analysis, the quantity of the compound of the contained 2-of having hydroxyl-3-chloropropyl is less than 1% (weight) in the slurry of acquisition.

Step (A) and (B) repeat 4 times is used for step (C) with the whole slurries that obtain.

Step (C): above-mentioned slurry and 24 liters of distilled water and 80 gram toluenesulfonic acid sodium salts are placed in the container stir light and slowly, precipitation sodium-chlor in the slurry is dissolved in the water of adding, allow the interior liquid of container leave standstill then, whole organic layers are reclaimed, obtain transparent liquid product.

Arrange a washing device, be used for washing this liquid product with drop.This washing device comprise one high 300 millimeters, interior diameter is 50 millimeters a glass main cylinder, be connected in the tubular reservoir of main cylinder upper end, be connected in another tubular reservoir of main cylinder lower end, cover the lid on last reservoir and extend to the rotating shaft of main cylinder lower end by this lid center.The internal diameter of last reservoir is almost identical with main cylinder, highly is 160 millimeters, and an outage is arranged at an upper portion thereof.By lid, be provided with a liquid supply tube, almost extend to the lower end of reservoir.The internal diameter of following reservoir is basic identical, and the degree of depth is 160 millimeters, in its bottom one outage is arranged.Middle part at following reservoir has a liquid supply tube almost to extend to the lower end of rotating shaft by its sidewall.Around rotating shaft, six dishes are housed, on each dish many holes are arranged, each dish is contained on the axle at interval with constant, is filled to the upper end of main cylinder from the rotating shaft lower end.On the internal side wall of main cylinder, width be housed be 15 millimeters ring baffle, be inserted between each dish.The diameter of each dish is 40 millimeters, a garter spring is housed below around it.Having some diameters on each dish is 2 millimeters aperture, and surperficial from it break-through is to its lower surface.The upper end of rotating shaft is connected in drive system, can drive it and do to come and go rotation.

Liquid product is introduced washing device, half-full until last reservoir, rotating shaft is rotated with 110 rev/mins speed.The aqueous solution that contains 0.33% weight of toluene sodium sulfonate and 3% weight percent phosphoric acid sodium dihydrogen with 0.078 liter/minute speed input, when the aqueous solution that contacts with liquid product begins after the outage discharge of last reservoir, liquid product begins from the bottom discharge of reservoir down, and unpurified liquid product is imported from the liquid supply tube on washing device top with 0.51 liter/minute speed.Soon the liquid product that reclaims after the beginning discharge opeing is returned in the holder that stores liquid product, because it also is not purified.The aqueous solution of observing input is dispersed in the Epicholorohydrin layer, and the formation size is 0.3 to 7 millimeter a drop.After beginning to discharge the transparent liquid of purifying, collect the liquid of the liquid of 20 liters of discharges as purifying.

Then, with the liquid of the toluenesulfonic acid sodium salt solution washing purifying of 0.03% weight.The liquid of purifying and the aqueous solution are imported continuously with the speed of 0.45 liter/minute and 0.19 liter/minute respectively, and the rotating speed of rotating shaft is 110 rev/mins, obtains second transparent liquid.The Epicholorohydrin layer that collection washing for the second time obtains is as the purification of liquid by step (C) purifying.This purification of liquid contains the Epicholorohydrin of 83% weight.

Step (D) will be put into one 10 liters of rotatory evaporators at 2 liters of purification of liquid of portion that step (C) obtains, and under reduced pressure 60 ℃ of start vaporizer Epicholorohydrins make vacuum tightness be reduced to 2mmHg gradually, and temperature is increased to 140 ℃ of continuation evaporations.Make liquid cooling obtain product, its epoxy equivalent (weight) is 102.

Embodiment 15

The scale of embodiment 6 steps (A) to (C) is amplified 10 times carries out.

Step (D): the collected purification of liquid of step (C) is handled in flasher, obtained the concentrated solution that Epicholorohydrin concentration is 70% (weight).With thin-film evaporator evaporometer chloropharin, it is removed from purification of liquid, obtain the isocyanuric acid three-glycidyl ester product that Epicholorohydrin concentration has reduced.

Used vaporizer comprises 315 millimeters of diameters, and the cylindrical shell that height is 735 millimeters is stamped a lid that has liquid-inlet and pneumatic outlet, in its bottom liquid exit is arranged.Around the cylindrical shell jacket layer is housed, makes heating medium circulation therein, cylindrical shell also is connected in the vacuum fan that condenser is housed by pneumatic outlet.In cylindrical shell, a rotating shaft of passing lid is arranged, be fixed with a diameter on the top of axle and be 275 millimeters dish, below dish, a coater is arranged, coater is clipped in the anchor clamps with certain interval, and anchor clamps are fixed on the end of the rod that is stretched out by rotating shaft.The device mode of coater is to make rotating shaft when rotation, and coater is subjected to centrifugal action to press to the inwall of cylindrical shell and slide along this inwall.The shape of coater is the rectangular parallelepiped of 600 millimeters long, faces the long in vertical direction of cylindrical shell, and width is 20 millimeters plane.On this plane, to the bottom, be carved with many grooves, these grooves and the sea line plane of crossing at 45 every 12 millimeters from the top.The degree of depth of groove is 8 millimeters, and width is 12 millimeters.

The vaporizer jacket layer is introduced in heating steam, and rotating shaft is rotated with 200 rev/mins speed, starts vacuum fan and makes pressure remain on 10mmHg.Is the liquid product concentrated solution of 70% weight with 22.4 kilograms/hour speed to vaporizer input Epicholorohydrin concentration, film thickness is 230 microns, mean residence time is 15 seconds, is that 123 ℃, epoxy equivalent (weight) are 103, contain the product of 2500ppm Epicholorohydrin from the recyclable temperature that obtains of the outlet of base of evaporator.

The product that obtains like this is transparent liquid, does not wherein have insoluble material.The product liquid that obtains is like this handled in vaporizer once more, obtained the lower product of Epicholorohydrin concentration.

When second takes turns operation, jacket layer is introduced in heating steam, rotating shaft is rotated with 200 rev/mins speed, starts vacuum fan and makes pressure remain on 0.2mmHg.Is 2 with 14.0 kilograms/hour speed to vaporizer input Epicholorohydrin concentration, the aforesaid liquid of 500ppm, film thickness is 170 microns, and mean residence time is 18 seconds, is that 155 ℃, epoxy equivalent (weight) are 103, contain the product of 54ppm Epicholorohydrin from the recyclable temperature that obtains of the outlet of base of evaporator.The product that reclaims is transparent liquid, does not wherein have insoluble material.Calculate according to the tricarbimide raw material, the productive rate of isocyanuric acid three-glycidyl ester is 90%.

Step (E): with the product fusion that the resulting Epicholorohydrin concentration of step (D) is 54ppm, get 100 gram melts and under agitation add gradually in the flask that 400 gram methyl alcohol are housed, form the methanol solution of this product.Solution is heated to the reflux temperature of methyl alcohol, was cooled to 5 ℃ through 12 hours again, make and be settled out white crystals in the solution.By filtering to isolate the crystal of white, its drying is obtained 82 gram final products, its epoxy equivalent (weight) is 99.

Embodiment 16

Make by step (A) and method (B) among the embodiment 13 and to contain the slurry that precipitates sodium-chlor.

Then whole slurries are handled under the speed that improves by the method for embodiment 14 step C.Sodium-chlor by in the dissolving removal slurry obtains liquid product, utilizes washing device, with this liquid product of solution washing of toluenesulfonic acid sodium salt and SODIUM PHOSPHATE, MONOBASIC, uses the toluenesulfonic acid sodium salt solution washing more earlier, obtains the liquid of purifying.With flasher purification of liquid is concentrated, obtain concentrated solution, remove Epicholorohydrin by the method for embodiment 15 steps (D) with thin-film evaporator again, obtain 27.0 kilograms of products, the epoxy equivalent (weight) of product is 101, and Epicholorohydrin concentration is 80ppm.

Embodiment 17

Step (C): the reagent wash slurry that need not purify with distilled water by the method for embodiment 1 at first.Washing is for the second time undertaken by the method for embodiment 1, and difference is to replace 2 gram toluenesulfonic acid sodium salts with 2 gram Sodium.beta.-phenylacrylates.

Last washing is undertaken by the method for embodiment 1, and difference is the liquid that obtains purifying with the solution of 0.1 gram Sodium.beta.-phenylacrylate in 800 gram distilled water.

Step (D): the method by embodiment 1 step (D) is handled the whole last Epicholorohydrin layer that obtains in step (C), is reclaimed by vaporizer and obtains 257 gram products, surveys less than chlorion in the product.Kaolin turbidity when the epoxy equivalent (weight) of product, 140 ℃ of fusions, in sealed vessel 150 ℃ down the epoxy equivalent (weight) of heating after 24 hours is all identical with the product that obtains among the embodiment 1.

Embodiment 18

Step (C): the reagent wash slurry that need not purify with distilled water by the method for embodiment 1 at first.Washing is for the second time undertaken by the method for embodiment 1, and difference is formaldehyde condensation products (people are referred to as water-soluble dehydrating agent) the replacement 2 gram toluenesulfonic acid sodium salts with 2 gram sodium naphthalene sulfonates.

Last washing is undertaken by the method for embodiment 1, and difference is the liquid that obtains purifying with the solution of formaldehyde condensation products in 800 gram distilled water of 0.1 gram sodium naphthalene sulfonate.

Embodiment 19

Step (C): at first press the method filtering stock of embodiment 1, difference is to replace 2 gram toluenesulfonic acid sodium salts with 0.1 gram disodium phthalate.Washing is for the second time undertaken by the method for embodiment 1, and difference is to replace 2 gram toluenesulfonic acid sodium salts with 0.5 gram disodium phthalate.

Last washing is undertaken by the method for embodiment 1, and difference is the liquid that obtains purifying with the solution of 0.1 gram disodium phthalate in 800 gram distilled water.

Step (D): the method by embodiment 1 step (D) is handled the whole last Epicholorohydrin layer that obtains in step (C), obtain 257 gram products by the vaporizer recovery, survey in the product less than chlorion, the kaolin turbidity when its epoxy equivalent (weight), 140 ℃ of fusions, in sealed vessel 150 ℃ the epoxy equivalent (weight) of heating after 24 hours is all identical with the product that obtains among the embodiment 1 down.

Embodiment 20

Step (C): at first press the method filtering stock of embodiment 1, difference is to replace 2 gram toluenesulfonic acid sodium salts with 0.2 gram salcylic acid disodium.Washing is for the second time undertaken by the method for embodiment 1, and difference is to replace 2 gram toluenesulfonic acid sodium salts with 0.5 gram salcylic acid disodium.

Last washing is undertaken by the method for embodiment 1, obtains the liquid of purifying.

Embodiment 21

Step (C): the reagent wash slurry that need not purify with distilled water by the method for embodiment 1 at first.Washing is for the second time undertaken by the method for embodiment 1, and difference is to replace 2 gram toluenesulfonic acid sodium salts with 2 gram sodium lauryl sulphate.

Last washing is undertaken by the method for embodiment 1, and difference is the liquid that obtains purifying with the solution of 0.2 gram sodium lauryl sulphate in 800 gram distilled water.

Use embodiment 13 steps (A) and (B) in used reactor, used washing device in embodiment 14 steps (C), with used thin-film evaporator in embodiment 15 steps (D), be raw material with the terephthalic acid, repeat embodiment 11 by the scale of amplifying 10 times.

Step (A) can successfully be undertaken by the method for embodiment 11.When step (B) was carried out, different with embodiment 11, sedimentary sodium-chlor did not accumulate and sticks on the sidewall of reactor, and it is evenly whole that reaction mixture keeps.The reaction mixture that obtains reclaims as slurry.

Do not use finishing agent in the step (C).After adding 60 kilograms of distilled water, whole slurries are stirred in container light and slowly, make that sedimentary sodium-chlor is dissolved in the added water in the slurry, and allow it leave standstill 12 hours.Reclaim whole organic layers, obtain transparent liquid product.At first press the method for embodiment 14, this transparent liquid product and washing are imported washing device with distilled water,, obtain transparent purification of liquid with this liquid product of distilled water wash.The liquid that reclaims is used distilled water wash again, obtains the purification of liquid of step (C).

Step (D) is undertaken by the method for embodiment 15.The liquid of described purifying is at first handled in flasher, obtain the concentrated solution that Epicholorohydrin concentration is 70% (weight), again concentrated solution is imported vaporizer, be 10mmHg at mean pressure for the first time, film thickness is 220 microns, mean residence time is to handle under 15 seconds the condition, obtaining temperature in the outlet of base of evaporator is 120 ℃, Epicholorohydrin content is the product of 2600ppm, for the second time be to be 0.2mmHg at mean pressure, film thickness is 180 microns, and mean residence time is to handle under 18 seconds the condition, obtaining 25.8 kilograms of temperature in the outlet of base of evaporator is 155 ℃, and Epicholorohydrin content is the product of 60ppm.

The epoxy equivalent (weight) of the product that obtains like this is 146, is the transparent liquid that does not wherein have insoluble material.

Embodiment 23

Use reactor among the embodiment 13 to carry out step (A) and (B), the thin-film evaporator among the use embodiment 15 carries out step (D).

Step (A): 1000 gram water, 250 grams are mixed the formation reaction mixture as the Sodium Bromide of catalyzer, 92.5 kilograms of Epicholorohydrins and 8.3 kilograms of terephthalic acids.Reaction mixture was heated to 120 ℃ through 12 hours under refluxing, the Epicholorohydrin of liquefaction is back in the reactor, and the water of liquefaction is discharged outside the reactor.Reaction mixture comes to life in 90 ℃ under barometric point.When the temperature of reaction mixture reaches 120 ℃, stop heating, allow it be cooled to 45 ℃ then, obtain reaction product.

Step (B): in remaining in 45 ℃ total overall reaction product, the sodium chloride aqueous solution that under agitation dropwise added 8.8 kilogram 50% (weight) through 6 hours, from the reaction mixture evaporation water outlet and the Epicholorohydrin of gained, Epicholorohydrin is back in the reactor, and water is expelled to outside the reactor.Dropping is to begin under the decompression of 100mmHg, and vacuum tightness improves gradually.In the dropping process, reaction mixture under agitation is owing to sedimentary sodium-chlor becomes muddiness, but maintenance is evenly whole.So obtain final slurry, sedimentary sodium-chlor can not accumulate or stick on the sidewall of reactor.

Step (C): after adding 3 kilograms of distilled water, whole slurries are stirred in container light and slowly, and allow it leave standstill 12 hours.Reclaim organic layer, it is transparent liquid, does not wherein contain sedimentary sodium-chlor.In all transparent liquid, add the biphosphate sodium water solution of 3 kilogram 5% (weight) then, the mixture of gained is stirred evenly, allow it leave standstill 6 hours.Reclaim organic layer, as the transparent liquid of purifying.We think in above-mentioned washing, make water and just can obtain transparent organic layer without finishing agent, be because in step (A) used catalyzer.

Step (D) is undertaken by the method for embodiment 15.The liquid of purifying is at first handled in flasher, obtain the concentrated solution that Epicholorohydrin concentration is 70% (weight), again concentrated solution is imported vaporizer, be 10mmHg at mean pressure for the first time, film thickness is 225 microns, mean residence time is to handle under 16 seconds the condition, obtaining temperature in the outlet of base of evaporator is 120 ℃, Epicholorohydrin content is the product of 2400ppm, for the second time be to be 0.2mmHg at mean pressure, film thickness is 175 microns, and mean residence time is to handle under 20 seconds the condition, obtaining 11.4 kilograms of temperature in the outlet of base of evaporator is 155 ℃, and Epicholorohydrin content is the product of 50ppm.

The epoxy equivalent (weight) of the product that obtains like this is 153, is the transparent liquid that does not wherein have insoluble material.

Embodiment 24

Step (A): use the used same reactor that agitator is housed among the embodiment 13,3 kg of water of packing into therein, 550 gram Tetramethylammonium chlorides, 138.8 kilograms of Epicholorohydrins and 12.9 kilograms of cyanuric acids stir and form reaction mixture.Under agitation the reacting by heating mixture raises its temperature.

When the temperature of reaction mixture reached 89 ℃, reaction mixture came to life under barometric point.Continue heating 5 hours, with the steam cooling that produces, the Epicholorohydrin of whole liquefaction is back in the reactor with condenser continuously, the water of liquefaction is discharged outside the reactor.When the temperature of reaction mixture reaches 120 ℃, stop heating, it is 45 ℃ reaction product that reaction mixture obtains temperature.In product, do not contain unreacted cyanuric acid.

Step (B): under the 100mmHg decompression, begin 25.6 kilograms of (counting 3.2 moles by NaOH) 50% (weight) aqueous sodium hydroxide are added in the above-mentioned reaction product that remains on 50 ℃, form reaction mixture, allow water and Epicholorohydrin from reaction mixture, be evaporated simultaneously.

Vacuum tightness is increased gradually, with steam cooling, the Epicholorohydrin of whole liquefaction is back in the reactor with condenser continuously, the water of liquefaction is discharged outside the reactor.When vacuum tightness reaches 60mmHg, stop to drip, obtain containing the slurry of sedimentary sodium-chlor.Dropping lasts 6 hours.In the dropping process, the reaction mixture under stirring is owing to sedimentary sodium-chlor becomes muddiness, but maintenance is evenly whole.Allowing refluxes continued 5 minutes again, removed the vacuum of reactor then, stopped to stir.

Press liquid-phase chromatographic analysis, the quantity of the compound of the contained 2-of having hydroxyl-3-chloropropyl is less than 1% (weight) in the slurry of acquisition.

Step (C): whole slurry washings that will obtain at step (B) three times.

At first, stir, left standstill then 24 hours with 90 kilograms water.Secondly, stir, left standstill then 24 hours with the biphosphate sodium water solution of 15 kilogram 5% (weight).At last, with 90 kg of water

At first, stir, left standstill then 24 hours with 90 kilograms water.Secondly, stir, left standstill then 24 hours with the biphosphate sodium water solution of 15 kilogram 5% (weight).At last, stir, left standstill again 24 hours with 90 kg of water.Last Epicholorohydrin layer reclaims the liquid as purifying.

Step (D): will put into a rotatory evaporator at the whole last Epicholorohydrin layer that step (C) obtains in batches, and under reduced pressure heat to remove Epicholorohydrin.Last 1 hour before stopping to evaporate is in 2mmHg pressure and 140 ℃ of heating.Make the material cooling in the vaporizer then, reclaim and obtain 26.7 kilograms of products.By the productive rate that calculates product is 90% (calculating according to raw material cyanuric acid used in the step (A)).

The epoxy equivalent (weight) of product is 104, is transparent when 140 ℃ of fusions.

Step (E): with the resulting product fusion of step (D), get 100 gram melts and under agitation add gradually in the flask that 400 gram methyl alcohol are housed, form the methanol solution of this product.Solution is heated to the reflux temperature of methyl alcohol, was cooled to 5 ℃ through 12 hours again, make and be settled out white crystals in the solution.By filtering to isolate the crystal of white, its drying is obtained 82 gram final products.The epoxy equivalent (weight) of final product is 100.

Comparative Examples 3

Step (A) and (B) undertaken by the method for embodiment 24, but what use is the reactor that blade is housed.In step (B), sedimentary sodium-chlor sticks to the sidewall of reactor, thereby reaction mixture can not keep even.Step (C) and (D) undertaken by the method for embodiment 24 is reclaimed by vaporizer and obtains 25.2 kilograms product.The epoxy equivalent (weight) of product is 109.Method by embodiment 24 steps (E) is handled this product, obtains 80 gram white crystals as the exsiccant final product.The epoxy equivalent (weight) of final product is 101.

Embodiment 25

Step (A): in 20 liters of glass reactors of the agitator that the band blade is housed, the 300 gram water of packing into, 55 gram Tetramethylammonium chlorides, 13.88 kilograms of Epicholorohydrins and 1.29 kilograms of cyanuric acids form reaction mixture.Under agitation the reacting by heating mixture raises its temperature.

When the temperature of reaction mixture reached 89 ℃, reaction mixture came to life under barometric point.Continue heating 5 hours, with the steam cooling that produces, the Epicholorohydrin of whole liquefaction is back in the reactor with condenser continuously, the water of liquefaction is discharged outside the reactor.When the temperature of reaction mixture reaches 120 ℃, stop heating, it is 45 ℃ reaction product that reaction mixture obtains temperature.In product, detect less than unreacted cyanuric acid.

Step (B): under 100mmHg pressure, begin 2.56 kilogram of 50% (weight) aqueous sodium hydroxide added in the above-mentioned reaction product that remains on 50 ℃, form reaction mixture, allow water and Epicholorohydrin from reaction mixture, be evaporated simultaneously.

Vacuum tightness is increased gradually, with steam cooling, the Epicholorohydrin of whole liquefaction is back in the reactor with condenser continuously, the water of liquefaction is discharged outside the reactor.When vacuum tightness reaches 60mmHg, stop to drip, obtain containing the slurry of sedimentary sodium-chlor.Dropping lasts 6 hours.Allowing refluxes continued 5 minutes again, removed the vacuum of reactor then, stopped to stir.

Step (A) and (B) repeat four times is used for step (C) with the whole slurries that obtained.

Step (C): above-mentioned liquid product is placed in the container stirs light and slowly, allow sedimentary sodium-chlor be dissolved in the added water, allow the liquid in the container leave standstill then, reclaim whole liquid product layers, obtain partially purified liquid product with 24 liters of distilled water.

Used washing device is further purified this liquid product among the use embodiment 14.

Partially purified liquid product is introduced washing device, half-full until last reservoir, rotating shaft is rotated with 110 rev/mins speed.The aqueous solution that contains 3% (weight) SODIUM PHOSPHATE, MONOBASIC with 0.078 liter/minute speed input, when the aqueous solution that contacts with liquid product begins after the outage discharge of last reservoir, liquid product begins from the bottom discharge of reservoir down, and unpurified liquid product is imported from the liquid supply tube on washing device top with 0.51 liter/minute speed.Soon the liquid product that reclaims after the beginning discharge opeing is returned in the holder that stores liquid product, because it also is not purified.The aqueous solution of observing input is dispersed in the Epicholorohydrin layer, and the formation size is 0.3 to 7 millimeter a drop.After beginning to discharge the transparent liquid of purifying, collect the liquid of the liquid of 20 liters of discharges as purifying.

Then, use the liquid of distilled water wash purifying.The liquid of purifying and water are imported continuously with the speed of 0.45 liter/minute and 0.19 liter/minute respectively, and the rotating speed of rotating shaft is 110 rev/mins, obtains the second transparent liquid product.The Epicholorohydrin layer that collection washing for the second time obtains is as the purification of liquid by step (C) purifying.The productive rate of triglycidyl isocyanurate is 90%.

Step (D): will put into one 10 liters of rotatory evaporators at 5 kilograms of liquid products of portion that step (C) obtains, under reduced pressure 60 ℃ of start vaporizers are removed Epicholorohydrin, when continuing evaporation vacuum tightness are increased to 4mmHg gradually, and fluid temperature is increased to 150 ℃.Gained liquid contains the Epicholorohydrin of 500ppm, and its epoxy equivalent (weight) is 104, is transparent when 140 ℃ of fusions.

Embodiment 26

Prepare the product liquid that contains sedimentary sodium-chlor by embodiment 25 steps (A) and method (B), difference is with 55 gram bromination ethyl triphenyl _ replacements 55 gram Tetramethylammonium chlorides.Step (A) and (B) repeat four times is used for step (C) with the whole slurries that obtain.

Step (C) is undertaken by the method for embodiment 25.At first obtain partially purified liquid product, with embodiment 14 used washing devices partially purified liquid product is purified to higher degree then.

When washing for the first time in washing device, rotating shaft is rotated continuously with 90 rev/mins speed.Import the biphosphate sodium water solution of 3% (weight) with 0.052 liter/minute speed by the liquid supply tube of following reservoir.After the aqueous solution that contacts with liquid product began to discharge from the outage of last reservoir, liquid product began to discharge from the bottom of reservoir down, and partially purified liquid product is imported from the washing device top with 0.34 liter/minute speed.Soon the liquid product that reclaims after the beginning discharge opeing is returned in the holder that stores liquid product.The biphosphate sodium water solution of observing input is dispersed in the Epicholorohydrin layer, and the formation size is 0.3 to 3 millimeter a drop.After beginning to discharge the transparent liquid that is purified to higher degree, collect the product liquid that the liquid conduct of all discharging is purified to higher degree.

Then, with the highly purified product liquid of distilled water wash.Product liquid and water are imported continuously with the speed of 0.30 liter/minute and 0.13 liter/minute respectively, and the rotating speed of rotating shaft is 90 rev/mins, obtains the second transparent liquid product.The Epicholorohydrin layer that collection washing for the second time obtains is as the highly purified product liquid that is obtained by step (C).

Step (D): the method by embodiment 25 will evaporate at the Epicholorohydrin in the liquid product that step (C) obtains, and obtaining pressure is 4mmHg, and temperature is 150 ℃ a product liquid.Gained liquid contains the Epicholorohydrin of 460ppm, and its epoxy equivalent (weight) is 105, is transparent when 140 ℃ of fusions.

Embodiment 27

Step (B): under 100mmHg pressure, begin 2.56 kilogram of 50% (weight) aqueous sodium hydroxide added in the above-mentioned total overall reaction product that remains on 50 ℃, form reaction mixture, allow water and Epicholorohydrin from reaction mixture, be evaporated simultaneously.

Vacuum tightness is increased gradually, with steam cooling, the Epicholorohydrin of whole liquefaction is back in the reactor with condenser continuously, the water of liquefaction is discharged outside the reactor.When vacuum tightness reaches 60mmHg, stop to drip, obtain containing the liquid product of sedimentary sodium-chlor.Dropping lasts 6 hours.Allowing refluxes continued 5 minutes again, removed the vacuum of reactor then, stopped to stir.

Step (C): whole liquid products that step (B) is obtained wash three times.At first, above-mentioned liquid product is stirred with 6 kilograms of distilled water, left standstill then 24 hours.Secondly, stir, left standstill again 24 hours with the biphosphate sodium water solution of 6 kilogram 5% (weight).At last, stir, left standstill then 24 hours with 8 kilograms of distilled water.Reclaim the liquid product of final Epicholorohydrin layer as purifying.

Step (D): the collected purification of liquid of step (C) is handled in flasher, obtained the concentrated solution that Epicholorohydrin concentration is 50% (weight).With vaporizer used among the embodiment 15 evaporometer chloropharin from the concentrated solution film, obtain the isocyanuric acid three-glycidyl ester product that Epicholorohydrin concentration has reduced.Calculate by used tricarbimide raw material, the productive rate of triglycidyl isocyanurate is 90%.

The vaporizer jacket layer is introduced in heating steam, and rotating shaft is rotated with 200 rev/mins speed, and starts vacuum fan.The Epicholorohydrin concentration that is obtained by flasher to the vaporizer input is the liquid product concentrated solution of 50% (weight).Feeding rate, vacuum tightness, film thickness (μ) and mean residence time during the vaporizer operation are as shown in table 1, by the product (p of base of evaporator recovery ₁) and (p ₂) having the temperature of base of evaporator outlet, its epoxy equivalent (weight) and Epicholorohydrin concentration (ECHppm) are also listed in table 1.Two products all are transparent liquid, wherein do not have insoluble material.

Then with the product liquid (p that reclaims ₁) in vaporizer, handle again, obtain the lower product (Q of Epicholorohydrin concentration ₁).At this moment, the input rate of liquid is 14.0 kilograms/hour, and the rotating speed of rotating shaft is 200 rev/mins.Feeding rate, vacuum tightness, film thickness and mean residence time during the vaporizer operation are as shown in table 1, by the product (Q of base of evaporator recovery ₁) having the temperature of base of evaporator outlet, its epoxy equivalent (weight) and Epicholorohydrin concentration (ECHppm) are also listed in table 1.The product of this recovery is transparent liquid, does not wherein have insoluble material.

Table 1

Evaporation conditions and product property	The product that reclaims
	The product that reclaims			P ₁	P ₂	Q ₁
	The liquid of input	Concentrated solution	Concentrated solution	P ₁	P ₂	Q ₁	P ₁
Defeated material speed (kilogram/hour)	The liquid of input	Concentrated solution	Concentrated solution	21.7	7.3	14.0	P ₁
Defeated material speed (kilogram/hour)	Vacuum tightness (mmHg)	10	10	21.7	7.3	14.0	0.2
Film thickness (micron)	Vacuum tightness (mmHg)	10	10	450	150	170	0.2
Film thickness (micron)	The residence time (second)	15	15	450	150	170	18
At exit product temperature (0 ℃)	The residence time (second)	15	15	120	137	150	18
At exit product temperature (0 ℃)	The epoxy equivalent (weight) of product	103	103	120	137	150	103
The Epicholorohydrin concentration (ppm) of product	The epoxy equivalent (weight) of product	103	103	3800	2000	80	103

Step (E): with the resultant product (Q of 100 gram steps (D) ₁) melts under agitation add gradually in the flask that 400 gram methyl alcohol are housed, form the methanol solution of this product.Solution is heated to the reflux temperature of methyl alcohol, was cooled to 5 ℃ through 12 hours again, make and be settled out white crystals in the solution.By filtering to isolate the crystal of white, its drying is obtained 82 gram final product (Z ₁), its epoxy equivalent (weight) is 99.

Comparative Examples 4

Obtain the liquid product of purifying by the method for embodiment 27, in flasher, handle then, obtain the concentrated solution that Epicholorohydrin concentration is 50% (weight).

5 kilograms of these concentrated solutions are put into one 10 liters of rotatory evaporators, remove Epicholorohydrin at 100mmHg pressure and 60 ℃ of following start vaporizers.Gas clean-up and elevated temperature gradually in continue removing the Epicholorohydrin process.Back 4 hours of evaporation beginning, the liquid in the vaporizer is under 4mmHg pressure, and temperature reaches 150 ℃.The liquid of gained contains the 500ppm Epicholorohydrin, and its epoxy equivalent (weight) is 104.Continued the evaporometer chloropharin 4 hours down lower 2mmHg pressure and 160 ℃, the liquid that obtains contains the 200ppm Epicholorohydrin, and its epoxy equivalent (weight) is increased to 107.

Embodiment 28

Using internal volume is 5 cubic metres reactor, repeats embodiment 24 with the scale of amplifying 25 times.

Step (A) can successfully be undertaken by the method for embodiment 24.In step (B), different with Comparative Examples 3, reaction mixture keeps evenly, and sedimentary sodium-chlor can not adhere on the sidewall of reactor.

Step (C) and (D) undertaken by the method for embodiment 24, the productive rate with 90% obtains product.The epoxy equivalent (weight) of product is 104.Step (E) is undertaken by the method for embodiment 24, and the productive rate with 82% obtains product.The epoxy equivalent (weight) of product is 100.

Embodiment 29

Make the slurry that contains sedimentary sodium-chlor by step (A) and method (B) among the embodiment 13.

Whole slurries are stirred with 90 kg of water light and slowly, make that sedimentary sodium-chlor is dissolved in the added water in the slurry, allow the liquid in the container leave standstill then.Reclaim whole organic layers, obtain transparent liquid.Utilize washing device used in embodiment 14 steps (C) with this liquid purifying again, at first use the aqueous solution that contains 3% (weight) SODIUM PHOSPHATE, MONOBASIC and do not contain toluenesulfonic acid sodium salt, use distilled water then, obtain the liquid of purifying.

The method of pressing embodiment 15 steps (D) with the liquid of this purifying of rate processing of improving, utilizes thin-film evaporator to remove Epicholorohydrin in flasher again, obtains 26.7 kilograms of epoxy equivalent (weight)s and be 104, Epicholorohydrin concentration is the product of 60ppm.This product is transparent at 140 ℃ melt.

According to the present invention, make 2 of compound compound or that contain 1-3 amido that contains 2-4 carboxyl, 3-epoxypropyl derivative or 2-methyl-2, the purified product of 3-epoxypropyl derivative.Product has high oxyethane oxygen level, and is quite transparent when fusion, and has very high thermostability, 150 ℃ the heating 24 hours after its epoxy equivalent (weight) constant.Product with high like this purity and thermostability can be used as the transparent encapsulant of semiconducter device (as luminescent device, episcotister spare or electrooptical device).

The method according to this invention, the product that can prepare above-mentioned purifying with high efficiency, for example, has high yield, epihalohydrin or 2-methyl epihalohydrin can have high-recovery at short notice, and be easy to handle by the waste water that present method produces, because it contains a spot of epihalohydrin or 2-methyl epihalohydrin and epoxy compounds.

Claims

1. a compound that contains 2-4 carboxyl or 1-3 amido from its molecule produces 2,3-epoxypropyl derivative or 2-methyl-2, the method of 3-epoxypropyl derivative purified product, wherein the carboxyl in the compound or all hydrogen atoms in the amido are all by 2,3-epoxypropyl or 2-methyl-2, the 3-epoxypropyl replaces, product has 1.0-1.1 times of epoxy equivalent (weight) and the 10ppm or the lower content of halide ions of the theoretical epoxy equivalent (weight) of derivative, when fusing, can form transparent liquid, increase by 3% when epoxy equivalent (weight) is maximum after 24 hours 150 ℃ of storages, the method is characterized in that it comprises step (A)-(D):

(A) make epihalohydrin or 2-methyl epihalohydrin and the compound reaction that 2-4 carboxyl or 1-3 amido are arranged, in reaction mixture, the ratio of compound and epihalohydrin or 2-methyl epihalohydrin is that per 1 mole of active hydrogen atom of the carboxyl of compound or amido is to 1.2-60 mole epihalohydrin or 2-methyl epihalohydrin, tertiary amine, quaternary ammonium hydroxide or the salt, three that also contain catalytic quantity replace phosphine or season _ salt, contain the 2-hydroxyl-3-halopropyl derivative of this compound or the reactor product of 2-hydroxy-2-methyl-3-halopropyl derivative thereby form;

(B) with the oxyhydroxide of 1-2 mole to the per 1 mole carboxyl of compound described in the reaction product before step (A) reaction or the ratio of the active hydrogen atom of amido, in reaction product, add alkali metal hydroxide gradually, to cause and to finish dehydrohalogenation is derivative, stir the slurry that contains sedimentary alkali metal halide that produces simultaneously, contain 2 of this compound thereby form, 3-epoxypropyl derivative or 2-methyl-2, the final slurry of 3-epoxypropyl derivative and the alkali metal halide that produces by dehydrohalogenation;

(C) be used as sulfonic acid, the sulfonate of finishing agent, the carboxylate salt that at least 7 carbon atoms are arranged, the sulfuric acid of alcohol that at least 4 carbon atoms are arranged or the aqueous solution of its mixture, come the final slurry of cleaning step (B) gained, or clean the product liquid from the final slurry of step (B) gained, removed alkali metal halide and to have obtained, described finishing agent has 1% weight solubleness at least in 30 ℃ of water, described solution contains the finishing agent that is used for refining slurry or product liquid of significant quantity, thereby forms the purification that contains the derivative that forms in step (B): and

2. the method for production derivative as claimed in claim 1, its feature is that also the method for carrying out step (B) is: adding hydroxide concentration in container is the aqueous solution of the alkali metal hydroxide of 20-70 weight %, under agitation keep slurry, make slurry generation circulation and rise to pulp surface from its bottom along container inner wall, make upwelling be reversed to downward eddy current again, and shearing eddy current, thereby keep the even of slurry, simultaneously at 10-80 ℃, evaporate under the vacuum, remove the water of adding and the water that reaction generates from slurry.

3. the method for production derivative as claimed in claim 1, its feature is that also the method for carrying out step (C) is: add described aqueous solution droplets in the product liquid tower, its mean diameter is the 0.1-10 millimeter, drop is risen, afterwards, in tower, assemble and form aqueous layer, progressively repeat in tower, to add the rising and the accumulative circulation of drop, drop, the aqueous solution is provided in product liquid continuously, per 100 weight part derivatives provide the finishing agent of 0.01-5 weight part in respect to product liquid, thus the purification product.

4. the method for production derivative as claimed in claim 1, its feature is that also the method for carrying out step (D) is: be coated with described purification at a substrate surface, form the film of purification or its enriched material, film thickness is the 30-500 micron, end at film, the concentration of the volatile constituent in purification or its enriched material is the highest, and reduce gradually, the relative the other end at film, concentration is minimum, at 100-165 ℃, is under 5mmHg or the lower condition at component pressure, from film evaporating volatile component, end at the film that its maximum concentration is arranged provides purification or its enriched material continuously simultaneously, under evaporation, makes liquid be sent to the relative the other end gradually, film thickness is increased, and reclaim the final liquid that has than low volatility component concentration from the relative the other end of film continuously.

5. the method for production derivative as claimed in claim 3, its feature also is to carry out the method for step (B): adding hydroxide concentration in container is the aqueous solution of the alkali metal hydroxide of 20-70 weight %, under agitation keep slurry, make slurry generation circulation and rise to pulp surface from its bottom along container inner wall, make upwelling be reversed to downward eddy current again, and shearing eddy current, thereby keep the even of slurry, simultaneously at 10-80 ℃, evaporate under the vacuum, remove the water of adding and the water that reaction generates from slurry.

6. the method for production derivative as claimed in claim 4, its feature is that also the method for carrying out step (C) is: add described aqueous solution droplets in the product liquid tower, its mean diameter is the 0.1-10 millimeter, drop is risen, afterwards, in tower, assemble and form aqueous layer, progressively repeat in tower, to add the rising and the accumulative circulation of drop, drop, the aqueous solution is provided in product liquid continuously, per 100 weight part derivatives provide the finishing agent of 0.01-5 weight part in respect to product liquid, thus the purification product.

7. the method for production derivative as claimed in claim 2, its feature is that also the method for carrying out step (D) is: in substrate surface coating purification, form the film of purification or its enriched material, film thickness is the 30-500 micron, end at film, the concentration of the volatile constituent in purification or its enriched material is the highest, and reduce gradually, the relative the other end at film, concentration is minimum, at 100-165 ℃, is under 5mmHg or the lower condition at component pressure, from film evaporating volatile component, end at the film that its maximum concentration is arranged provides purification or its enriched material continuously simultaneously, under evaporation, makes liquid be sent to the relative the other end gradually, film thickness is increased, and reclaim the final liquid that has than low volatility component concentration from the relative the other end of film continuously.

8. the method for production derivative as claimed in claim 2, its feature is that also the method for carrying out cleaning liquid product in the step (C) is: add described aqueous solution droplets in the product liquid tower, its mean diameter is the 0.1-10 millimeter, drop is risen, afterwards, in tower, assemble and form aqueous layer, progressively repeat in tower, to add the rising and the accumulative circulation of drop, drop, the aqueous solution is provided in product liquid continuously, per 100 weight part derivatives provide the finishing agent of 0.01-5 weight part in respect to product liquid, thus the purification product; And the method for carrying out the evaporation in the step (D) is: in substrate surface coating purification, form the film of purification or its enriched material, film thickness is the 30-500 micron, end at film, the concentration of the volatile constituent in purification or its enriched material is the highest, reduce gradually along film, the relative the other end at film, concentration is minimum, at 100-165 ℃, at component pressure is under 5mmHg or the lower condition, and from film evaporating volatile component, the end at the film that its maximum concentration is arranged provides purification or its enriched material continuously simultaneously, under evaporation, make liquid be sent to the relative the other end gradually and film thickness is increased, and reclaim the final liquid that has than low volatility component concentration from the relative the other end of film continuously.

9. as the method for the described production derivative of arbitrary claim among the claim 1-8, its feature also is to carry out continuously the reaction in the step (A), in reaction mixture 90% or more active hydrogen atom disappear.

10. as the method for the described production derivative of arbitrary claim among the claim 1-8, its feature is that also the finishing agent in step (C) is polycondensate, tetrahydrophthalic acid, lauryl sulfate, phthalic acid, Whitfield's ointment or the styracin of Phenylsulfonic acid or toluenesulphonic acids or benzene sulfonate or tosylate, vinyl sulfonic acid, vinyl sulfonic acid polymkeric substance, naphthene sulfonic acid and formaldehyde.

11. method as the described production derivative of arbitrary claim among the claim 1-8, its feature is that also the compound described in the step (A) is a terephthalic acid, derivative in step (D) is a terephthalic acid two (2,3 epoxypropyl) ester or terephthalic acid two (2-methyl-2,3-epoxypropyl) ester.

12. method as the described production derivative of arbitrary claim among the claim 1-8, its feature is that also the compound described in the step (A) is an isocyanuric acid, derivative in step (D) is an isocyanuric acid three (2,3 epoxypropyl) ester or isocyanuric acid three (2-methyl-2,3-epoxypropyl) ester.

13. method as claimed in claim 11 is characterized in that also comprising after the step (D) following step (E):

(E) product that obtains in the step (D) is dissolved in the solvent, forms the solution of product, go out the crystal derivative, from solution, take out throw out and dry again from solution precipitation.

14. method as claimed in claim 12, step (E) below it is characterized in that after step (D), also comprising:

15. produce isocyanuric acid three (2 for one kind, the 3-epoxypropyl) ester or isocyanuric acid three (2-methyl-2, the 3-epoxypropyl) method of the purified product of ester, the epoxy equivalent (weight) of purified product be isocyanuric acid ester theoretical epoxy equivalent (weight) 1.0-1.1 doubly, when fusing, can form transparent liquid, the method is characterized in that it comprises step (A)-(D):

(A) make the reaction of epihalohydrin or 2-methyl epihalohydrin and isocyanuric acid, in reaction mixture, contain isocyanuric acid and epihalohydrin or 2-methyl epihalohydrin, its ratio is that the active hydrogen atom of 1 mole of isocyanuric acid is to 1.2-60 mole epihalohydrin or 2-methyl epihalohydrin, and contain the tertiary amine of catalytic quantity, quaternary ammonium hydroxide or salt, three replace phosphine or season _ salt, thereby form the reaction product that contains isocyanuric acid three (2-hydroxyl-3-halopropyl) ester or isocyanuric acid three (2-hydroxy-2-methyl-3-halopropyl) ester

(B) with the oxyhydroxide of 1-2 mole ratio to 1 mole of active hydrogen atom of the isocyanuric acid in the reaction product before the reaction of step (A), adding concentration in reaction product gradually is the alkali metal hydroxide aqueous solution of the oxyhydroxide of 20-70 weight %, to cause and to finish the dehydrohalogenation of the isocyanuric acid in the reaction product, formation contains the slurry of sedimentary alkali metal halide, under agitation keep simultaneously slurry, make slurry generation circulation and rise to pulp surface from its bottom along container inner wall, make upwelling be reversed to downward eddy current again, and shearing eddy current, thereby keep the even of slurry, and at 10-80 ℃, evaporate under the vacuum, remove the water of adding and the water that reaction generates from slurry, contain isocyanuric acid three (2 thereby form, the 3-epoxypropyl) the final slurry of the alkali metal halide of ester or isocyanuric acid three (2-methyl-2,3-epoxypropyl) ester and reaction generation

(C) water cleans the final slurry that obtains in step (B) or removes alkali metal halide and the product liquid that obtains from the final slurry of step (B), thus form the purification that contains isocyanuric acid ester and

(D) remove in step (C) epihalohydrin or 2-methyl epihalohydrin in the purification that obtains by evaporation, thereby form the purified product of isocyanuric acid three (2, the 3-epoxypropyl) ester or isocyanuric acid three (2-methyl-2,3-epoxypropyl) ester.

16. produce isocyanuric acid three (2 for one kind, the 3-epoxypropyl) ester or isocyanuric acid three (2-methyl-2, the 3-epoxypropyl) method of the purified product of ester, the epoxy equivalent (weight) of purified product be isocyanuric acid ester theoretical epoxy equivalent (weight) 1.0-1.1 doubly, when fusing, can form transparent liquid, the method is characterized in that it comprises step (A)-(D):

(B) with the oxyhydroxide of 1-2 mole ratio to 1 mole of active hydrogen atom of the isocyanuric acid in the reaction product before the reaction of step (A), adding concentration in reaction product gradually is the alkali metal hydroxide aqueous solution of the oxyhydroxide of 20-70 weight %, to cause and to finish the dehydrohalogenation of the isocyanuric acid in the reaction product, stir the slurry that contains sedimentary alkali metal halide simultaneously, contain isocyanuric acid three (2 thereby form, the 3-epoxypropyl) ester or isocyanuric acid three (2-methyl-2, the 3-epoxypropyl) the final slurry of the alkali metal halide of ester and reaction generation

(C) in the product liquid tower, add water droplet, its mean diameter is the 0.1-10 millimeter, water droplet is risen, afterwards, in tower, assemble and form water layer, progressively repeat in tower, to add the rising and the accumulative circulation of water droplet, water droplet, water is provided in product liquid continuously, per 100 weight part isocyanuric acid esters provide the water of 50-5000 weight part in respect to product liquid, come water to clean like this and remove the product liquid that alkali metal halide obtains from the final slurry of step (B), thereby form the purification contain isocyanuric acid ester and

17. produce isocyanuric acid three (2 for one kind, the 3-epoxypropyl) ester or isocyanuric acid three (2-methyl-2, the 3-epoxypropyl) method of the purified product of ester, the epoxy equivalent (weight) of purified product be isocyanuric acid ester theoretical epoxy equivalent (weight) 1.0-1.1 doubly, when fusing, can form transparent liquid, the method is characterized in that it comprises step (A)-(D):

(C) water cleans the final slurry that obtains in step (B) or removes the product liquid that alkali metal halide obtains from the final slurry of step (B), thus form the purification that contains isocyanuric acid ester and

(D) in substrate surface coating purification, form the film of purification or its enriched material, film thickness is the 30-500 micron, end at film, the concentration of the volatile constituent in purification or its enriched material is the highest, reduce gradually along film, the relative the other end at film, concentration is minimum, at 100-165 ℃, at component pressure is under 5mmHg or the lower condition, and from film evaporating volatile component, the end at the film that its maximum concentration is arranged provides purification or its enriched material continuously simultaneously, under evaporation, make liquid be sent to the relative the other end gradually and film thickness is increased, and reclaim the final liquid that has than low volatility component concentration from the relative the other end of film continuously, remove epihalohydrin or 2-methyl epihalohydrin in the purification that in step (C), obtains like this, thereby form the purified product of isocyanuric acid three (2, the 3-epoxypropyl) ester or isocyanuric acid three (2-methyl-2,3-epoxypropyl) ester.

18. production isocyanuric acid three (2 as claimed in claim 15, the 3-epoxypropyl) ester or isocyanuric acid three (2-methyl-2, the 3-epoxypropyl) method of ester, the method that its feature also is to carry out the cleaning of step (C) is: add water droplet in the product liquid tower, its mean diameter is the 0.1-10 millimeter, water droplet is risen, afterwards, in tower, assemble and form water layer, progressively repeat in tower, to add water droplet, the rising of water droplet and accumulative circulation, water is provided in product liquid continuously, and per 100 weight part isocyanuric acids provide the water of 50-5000 weight part in respect to product liquid, thereby form the purification that contains isocyanuric acid ester.

19. as claim 15, the described production isocyanuric acid three (2 of arbitrary claim in 16 or 18, the 3-epoxypropyl) ester or isocyanuric acid three (2-methyl-2, the 3-epoxypropyl) method of ester, its feature is that also the method for carrying out evaporation in the step (D) is: at substrate surface coating purification or its enriched material, form the film of purification or its enriched material, film thickness is the 30-500 micron, end at film, the concentration of the volatile constituent in purification or its enriched material is the highest, reduce gradually along film, the relative the other end at film, concentration is minimum, at 100-165 ℃, at component pressure is under 5mmHg or the lower condition, from film evaporating volatile component, end at the film that its maximum concentration is arranged provides purification or its enriched material continuously simultaneously, under evaporation, make liquid be sent to the relative the other end gradually, film thickness is increased, and continuously reclaim the final liquid that has than low volatility component concentration from the relative the other end of film, thereby form the purified product of isocyanuric acid three (2, the 3-epoxypropyl) ester or isocyanuric acid three (2-methyl-2,3-epoxypropyl) ester.

20. a method of producing isocyanuric acid three (2, the 3-epoxypropyl) ester or isocyanuric acid three (2-methyl-2,3-epoxypropyl) ester, step (E) below step (D) back that it is characterized in that its arbitrary claim in claim 15-19 increases:

(E) product that will obtain in step (D) is dissolved in the solvent, forms the solution of product, goes out the crystal derivative from solution precipitation, takes out throw out and dry again from solution, thereby forms the product that purity is higher than the product of step (D).

21. produce terephthalic acid two (2 for one kind, the 3-epoxypropyl) ester or terephthalic acid two (2-methyl-2, the 3-epoxypropyl) method of the purified product of ester, the epoxy equivalent (weight) of purified product be terephthalic acid theoretical epoxy equivalent (weight) 1.0-1.1 doubly, can form transparent liquid when fusing, described method is characterised in that it comprises step (A)-(D):

(A) make epihalohydrin or 2-methyl epihalohydrin and terephthaldehyde's acid-respons, in reaction mixture, contain terephthalic acid and epihalohydrin or 2-methyl epihalohydrin, its ratio is that the active hydrogen atom of 1 mole of terephthalic acid is to 1.2-60 mole epihalohydrin or 2-methyl epihalohydrin, and contain the tertiary amine of catalytic quantity, quaternary ammonium hydroxide or salt, three replace phosphine or season _ salt, thereby form the reaction product that contains terephthalic acid two (2-hydroxyl-3-halopropyl) ester or terephthalic acid two (2-hydroxy-2-methyl-3-halopropyl) ester

(B) with the oxyhydroxide of 1-2 mole ratio to 1 mole of active hydrogen atom of the terephthalic acid in the reaction product before the reaction of step (A), adding concentration in reaction product gradually is the alkali metal hydroxide aqueous solution of the oxyhydroxide of 20-70 weight %, to cause and to finish the dehydrohalogenation of the terephthalate in the reaction product, formation contains the slurry of sedimentary alkali metal halide, under agitation keep simultaneously slurry, make slurry generation circulation and rise to pulp surface from its bottom along container inner wall, make upwelling be reversed to downward eddy current again, and shearing eddy current, thereby keep the even of slurry, and at 10-80 ℃, evaporate under the vacuum, remove the water of adding and the water that reaction generates from slurry, contain terephthalic acid two (2 thereby form, the 3-epoxypropyl) the final slurry of the alkali metal halide of ester or terephthalic acid two (2-methyl-2,3-epoxypropyl) ester and reaction generation

(C) water cleans the final slurry that obtains in step (B) or removes alkali metal halide and the product liquid that obtains from the final slurry of step (B), thus form the purification that contains terephthalate and

(D) remove in step (C) epihalohydrin or 2-methyl epihalohydrin in the purification that obtains by evaporation, thereby form the purified product of terephthalic acid two (2, the 3-epoxypropyl) ester or terephthalic acid two (2-methyl-2,3-epoxypropyl) ester.

22. produce terephthalic acid two (2 for one kind, the 3-epoxypropyl) ester or terephthalic acid two (2-methyl-2, the 3-epoxypropyl) method of the purified product of ester, the epoxy equivalent (weight) of purified product be terephthalate theoretical epoxy equivalent (weight) 1.0-1.1 doubly, when fusing, can form transparent liquid, the method is characterized in that it comprises step (A)-(D):

(B) with the oxyhydroxide of 1-2 mole ratio to 1 mole of active hydrogen atom of the terephthalic acid in the reaction product before the reaction of step (A), adding concentration in reaction product gradually is the alkali metal hydroxide aqueous solution of the oxyhydroxide of 20-70 weight %, to cause and to finish the dehydrohalogenation of the terephthalic acid in the reaction product, stir the slurry that contains sedimentary alkali metal halide simultaneously, contain terephthalic acid two (2 thereby form, the 3-epoxypropyl) ester or terephthalic acid two (2-methyl-2, the 3-epoxypropyl) the final slurry of the alkali metal halide of ester and reaction generation

(C) in the product liquid tower, add water droplet, its mean diameter is the 0.1-10 millimeter, water droplet is risen, afterwards, in tower, assemble and form water layer, progressively repeat in tower, to add the rising and the accumulative circulation of water droplet, water droplet, water is provided in product liquid continuously, per 100 weight part terephthalate provide the water of 50-5000 weight part in respect to product liquid, come water to clean like this and remove the product liquid that alkali metal halide obtains from the final slurry of step (B), thereby form the purification contain terephthalate and

23. produce terephthalic acid two (2 for one kind, the 3-epoxypropyl) ester or terephthalic acid two (2-methyl-2, the 3-epoxypropyl) method of the purified product of ester, the epoxy equivalent (weight) of purified product be terephthalate theoretical epoxy equivalent (weight) 1.0-1.1 doubly, when fusing, can form transparent liquid, the method is characterized in that it comprises step (A)-(D):

(C) water cleans the final slurry that obtains in step (B) or removes the product liquid that alkali metal halide obtains from the final slurry of step (B), thus form the purification that contains terephthalate and

(D) in substrate surface coating purification, form the film of purification or its enriched material, film thickness is the 30-500 micron, end at film, the concentration of the volatile constituent in purification or its enriched material is the highest, reduce gradually along film, the relative the other end at film, concentration is minimum, at 100-165 ℃, at component pressure is under 5mmHg or the lower condition, and from film evaporating volatile component, the end at the film that its maximum concentration is arranged provides purification or its enriched material continuously simultaneously, under evaporation, make liquid be sent to the relative the other end gradually and film thickness is increased, and reclaim the final liquid that has than low volatility component concentration from the relative the other end of film continuously, remove epihalohydrin or 2-methyl epihalohydrin in the purification that in step (C), obtains like this, thereby form the purified product of terephthalic acid two (2, the 3-epoxypropyl) ester or terephthalic acid two (2-methyl-2,3-epoxypropyl) ester.

24. production terephthalic acid two (2 as claimed in claim 21, the 3-epoxypropyl) ester or terephthalic acid two (2-methyl-2, the 3-epoxypropyl) method of ester, the method that its feature also is to carry out the cleaning of step (C) is: add water droplet in the product liquid tower, its mean diameter is the 0.1-10 millimeter, water droplet is risen, afterwards, in tower, assemble and form water layer, progressively repeat in tower, to add water droplet, the rising of water droplet and accumulative circulation, water is provided in product liquid continuously, and per 100 weight part terephthalic acids provide the water of 50-5000 weight part in respect to product liquid, thereby form the purification that contains terephthalate.

25. as claim 21, the described production terephthalic acid two (2 of arbitrary claim in 22 or 24, the 3-epoxypropyl) ester or terephthalic acid two (2-methyl-2, the 3-epoxypropyl) method of ester, the method that its feature also is to carry out the evaporation of step (D) is: at substrate surface coating purification or its enriched material, form the film of purification or its enriched material, film thickness is the 30-500 micron, end at film, the concentration of the volatile constituent in purification or its enriched material is the highest, reduce gradually along film, the relative the other end at film, concentration is minimum, at 100-165 ℃, at component pressure is under 5mmHg or the lower condition, from film evaporating volatile component, end at the film that its maximum concentration is arranged provides purification or its enriched material continuously simultaneously, under evaporation, make liquid be sent to the relative the other end gradually, film thickness is increased, and continuously reclaim the final liquid that has than low volatility component concentration from the relative the other end of film, thereby form the purified product of terephthalic acid two (2, the 3-epoxypropyl) ester or terephthalic acid two (2-methyl-2,3-epoxypropyl) ester.

26. a method of producing terephthalic acid two (2, the 3-epoxypropyl) ester or terephthalic acid two (2-methyl-2,3-epoxypropyl) ester, step (E) below step (D) back that it is characterized in that its arbitrary claim in claim 21-25 increases:

(E) product that obtains in the step (D) is dissolved in the solvent, forms the solution of product, go out the crystal derivative, from solution, take out throw out and dry again, thereby form the product that purity is higher than the product of step (D) from solution precipitation.